JPH07329197A - Vehicle, honeycomb laminar structure, interior fittings, architecture and panel - Google Patents

Abstract

PURPOSE:To inhibit the generation of a poisonous gas from combustion and minimize the combustion of a material which is a source of poisonous gas by using an inorganic filament-reinforced ceramic material, at least, as an interior wall material and flooring. CONSTITUTION:An inorganic filament-reinforced ceramic material is used on a vehicle, the interior wall of an architecture and as flooring. The inorganic filament-reinforced ceramic material is a radical-polymerizable monomer consisting of fine metal oxide powder with an average grain diameter of 1mum or less as component A, a soluble cyclohexane polymer with a double chain structure as a component B, a 3-functional silane compound containing an ethylenically unsaturated double bond at least, in a single molecule as a component C, and an ethylene unsaturated double bond at least, in two molecules as a component E. A tow of inorganic fibers or a finished product thereof is impregnated with a liquid or a sheet-like product of a matrix composition containing these components A to E, or subjected to thermal permeation to form a prefreg which is then cured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to vehicles, buildings, and laminated structures, interior parts, and panels used therein.

[0002]

2. Description of the Related Art It is important to ensure the safety of passengers from fires in vehicles such as aircraft, automobiles and trains and buildings such as houses, warehouses, buildings and various storage facilities. The main causes of aircraft accidents, such as vehicle fires, are engine ignition, electrical wiring leaks,
It is a fire caused by contact with the ground during landing. The main cause of automobile fire accidents is ignition of gasoline due to sparks of electric systems due to impact of collision. The cause of train fire is ignition of flammable materials by sparks on overhead lines. Fires in buildings include fires in kitchens, fires from stoves in living rooms, fires from oil tanks, and fires from combustibles in a combustibles storage room.

In order to protect personnel from these fire accidents, flame retardation or nonflammability of various materials constituting vehicles or buildings has been promoted.

However, most of the materials called flame-retarded or non-combustible are made of plastic, so they are self-extinguishing, but they burn at high temperatures. Further, the flame-retardant material and the resin containing halogen mixed therein generate various toxic gases. Therefore, although the conventional flame-retardant synthetic resin composition or non-combustible synthetic resin composition is burnt or non-combustible, it is eventually burned, which causes a fire.

The problem here is how to delay the combustion of the material if it is finally burned, and to delay the combustion without generation of toxic gas.

[0006] For example, when an aircraft causes a fire accident on land or at sea, if there is a time of 2 minutes for the fire to spread to the passenger, the passenger may escape from the aircraft. It is said that the damage to passengers can be minimized.

Federal Aviation Administration,
Department of Transport Reguration # 25.803
90 in case of emergency
There is a safety standard that requires you to be able to escape within seconds.

As described above, safety standards for personnel such as passengers and passengers against fire are extremely strict in aircraft, and therefore various materials used in aircraft are required to have sufficient characteristics to meet the above safety standards. Is done.

The idea that such safety standards for passengers and passengers should be applied not only to aircraft but also to general vehicles such as vehicles, automobiles, and trains is a natural cause of the increasing awareness of safety in Japan. Be led to. Therefore, it is desired that various types of vehicles such as aircrafts are made of a material that suppresses the generation of toxic gas as much as possible and delays the start of combustion as much as possible.

Panels are used in various parts or inner walls of various vehicles such as aircraft. The original function of this panel is to have impact resistance and sound insulation. Panels in aircraft and the like are also required to function as heat insulating materials. Conventional panels are honeycomb, FR
It is configured using a P plate or a laminated body thereof.

The wall of an aircraft cabin (normally the cabin is located in the fuselage of the aircraft) has a honeycomb made of glass fiber and phenol resin, an epoxy resin plate material provided on the interior surface of the interior, and the outermost layer on the interior side. It is formed of a decorative plastic film or the like provided as.

However, at the time of a fire, the phenol resin is relatively hard to burn, but gas is generated at a high temperature, and the epoxy resin and the interior film are easily burned, so that the fire resistance is not yet perfect.

Under the circumstances, the present inventors have proposed a vehicle formed of a material capable of suppressing generation of toxic gas during combustion and suppressing combustion of the material as much as possible.
Generation of toxic gas during combustion can be suppressed as much as possible, combustion of the material can be suppressed as much as possible, laminated structure suitable as a constituent material of a vehicle, generation of toxic gas during combustion can be suppressed as much as possible, and combustion of the material can be suppressed. The aim was to develop interiors for vehicles or buildings that can be suppressed as much as possible, panels, and buildings that can suppress the generation of toxic gas during combustion and the combustion of the materials as much as possible.

Therefore, the inventor first focused on ceramics.

Ceramics are lighter in weight than metals. Therefore, ceramics are more suitable than metals as materials used in vehicles for achieving weight reduction. Metals generally have good thermal conductivity,
Ceramics have low thermal conductivity. Metals generate heat at high temperatures and oxidize, whereas ceramics do not. Therefore, ceramics are superior to metals in terms of protection from fire.

Ceramics have the advantage of being superior in heat resistance, high temperature strength, oxidation resistance, wear resistance and the like to organic materials or metal materials, but have the drawback of low fracture toughness. As a method of improving fracture toughness without losing the advantages of ceramics, that is, toughening, a particle dispersion method, whiskers or short fiber reinforced method, and long fiber reinforced method are being studied.

However, the particle dispersion method and the whisker strengthening method have a drawback in that even if the toughening can be achieved, if the fracture occurs in a very small portion, the entire fracture proceeds at once.

On the other hand, the long fiber reinforced method has a greater effect of improving fracture toughness than other methods, and in the long fiber reinforced ceramics, the fiber bears the load even if a load is applied. Destruction does not progress at once, and you can predict destruction before it completely destroys. This predictability of destruction is a great practical advantage.

However, when adopting the reinforcing method with long fibers, long fibers which retain sufficient strength even at temperatures of 1,200 ° C. or higher in air and 1,400 ° C. or higher in an inert atmosphere are still in practical use. Is not, therefore,
It is desired to develop a method capable of producing a composite at 1,200 ° C or lower, preferably 1,000 ° C or lower.

Producing the composite at a low temperature in this way can naturally be expected to greatly reduce the cost. Further, in order to produce a product having a curved shape or a complicated shape, a method of laminating and molding a prepreg having good tack property and drape property, as used in the production of carbon fiber / epoxy composites and the like. Is desirable. Furthermore, for industrial production, the firing operation can be carried out in air without replacement with an inert atmosphere or vacuum, and the molded body is in a free-standing state, that is, under unconstrained conditions. It is, of course, advantageous to be able to fire at.

Chemical vapor deposition and direct metal oxidation are known methods for producing fiber-reinforced ceramics by directly forming a ceramic matrix between fibers. These methods can be applied not only to long fiber bundles and their products, but also to aggregates of short fibers or whiskers.

The chemical vapor deposition method is a method of depositing and depositing ceramics to serve as a matrix in a bundle of fibers or a gap between preforms by chemical vapor deposition (CVI) (for example, J.
See T. Hoyt et al., SAMPE J. 27 No. 2, P11 (1991)). This method has a relatively low temperature, for example, 1,000 to
Although there is an advantage that a ceramic matrix is formed at 1,200 ° C., it takes a long time, for example, 100 hours to form the matrix, the void generation rate (void ratio) is high, and it is difficult to cope with complicated shapes. There's a problem.

The metal oxidation (Directed Metal Oxidation) method is a method in which a molten metal is brought into contact with a preform of reinforcing fibers, and the metal is converted into ceramics by oxidation and nitriding. This method is described, for example, in MS Newkirk et al., J. Mat.
er. Sci., are described, for example, 1 81 (1986). Although this method has the advantage that various ceramic matrices can be formed by changing the metal and the heating atmosphere, the metal remains in the product, which tends to reduce its strength at high temperatures. Further, this method also has a large limitation in manufacturing a product having a complicated shape.

A prepreg that is traditionally used in the composite material industry is used, and the prepreg is laminated, molded into a predetermined shape to obtain a product shape, and then fired to convert the matrix component into a ceramic body. Known methods for producing reinforced ceramics include a slurry impregnation method, a sol-gel method, and a polymer pyrolysis method.

The slurry impregnation method is a method in which fibers are impregnated with a slurry liquid containing ceramic fine particles and a binder such as an organic polymer to prepare a prepreg, which is debindered and then hot pressed in an inert atmosphere. This method is described, for example, in CA Doughan et al., Ceram. Eng. Sci. Pro.
c., 10 912 (1989). According to this method, there is an advantage that a fiber reinforced ceramic product having excellent mechanical properties can be produced, but 1,5
High temperature of 00 to 1,800 ℃ and 100 to 350k
A high pressure of g / cm ² is required, and deterioration of reinforcing fibers other than carbon fibers cannot be avoided. In addition, organic substances are carbonized at the time of debinding to volatilize and / or heat-shrink, so that the matrix performance is deteriorated and cracks and voids are generated.

In this method, water, which is inexpensive and easy to remove due to its low boiling point, is used as a medium in many examples. However, water is strong against a ceramic raw material such as a metal oxide. There is the problem that they have a tendency to adsorb, which makes this adsorbed water not easily removed by heating. Note that this prepreg does not have tackiness.

The sol-gel method is generally carried out by adding a metal alkoxide, which is a liquid raw material, in the presence of an acid or an alkali.
It is a method of converting a sol state to a gel state by hydrolysis and condensation and further applying heat to form ceramics. With this method, it is possible to form a ceramic even at a low temperature of 1,000 ° C. or less.

However, the disadvantage of this method is the generation of voids, cracks and fractures due to the large volume shrinkage when converting the wet gel to the dry gel and the shrinkage during firing. That is, the volume shrinkage may reach several tens of percent in some cases, so that cracks are generated between the fibers and the fibers that do not shrink (see Japanese Patent Laid-Open No. 63-282131).

In the polymer pyrolysis method, an organometallic polymer such as polycarbosilane or polysilazane is used as a matrix precursor, which is impregnated into fibers to prepare a prepreg, which is laminated, cured and then fired. It is a method of converting to a ceramic matrix. This method has been published for example Kiyoto Okamura, such as in Japan composite material Journal 11 99 (1985). This method has an advantage that it can be converted into ceramics even at a temperature of 1,200 ° C. or lower, but it also causes considerable shrinkage when the organometallic polymer is converted into a ceramic composition by thermal decomposition. In addition, these organometallic polymers cannot provide the required tackiness, and thus have a problem in shapeability.

The following reports and inventions have been published as examples of producing long fiber reinforced ceramics by applying the above three methods.

M. Chen et al. Mainly used boehmite (Boemite).
) And an alumina powder having a diameter of 0.5 μm are impregnated into carbon fibers or silicon carbide fibers, dried at 50 ° C. for 20 hours, heated to 1,000 ° C. under a nitrogen atmosphere, and heated. Then, the fiber-reinforced ceramics was prepared by cooling, and hot pressing at 1,200 ° C. using a graphite die. It was concluded that the composite thus obtained was porous, and its cause was the large shrinkage during heating and sintering (ECCM-3 Proceedings, p89 20-2).
3 March (1989)).

FI Hurwitz et al. Prepared a prepreg by a filament winding method using polysilsesquioxane as a matrix precursor and silicon carbide fibers as reinforcing fibers. The prepreg was stacked in a metal die, and the obtained laminate was heated at 70 ° C. and 689 Pa for 2 hours, and further heated and held at 180 ° C. for 1.5 hours. The laminated body was taken out from the die and was put under an argon gas flow to produce 525
Heated to ℃, 1,000 ℃ or 1,200 ℃. They found that the heat shrinkage during this heating was 19% for polyvinyl (50) methyl (50) silsesquioxane and 13% for polyphenyl (50) methyl (50) silsesquioxane.
And the formation of numerous cracks on the matrix surface and in the interfiber matrix region (Ceram. Eng. Sci.
Proc., 10 750 (1989)).

Frank Kung Ji et al. Made a prepreg by impregnating a high modulus fiber with a thermosetting organosilicone resin dissolved in an organic solvent, and partially cured the prepreg at a temperature not higher than 300 ° C. ( B-Staging), curing, post-curing, and then firing at a temperature of at least 1,000 ° C. in an inert atmosphere or under vacuum, a method for producing fiber-reinforced ceramics is disclosed (JP-B-63). -16350).

They also impregnate high modulus fibers with a mixture of an organic silsesquioxane sol and a colloidal metal oxide or mixture thereof or an organic silsesquioxane sol and a metal alkoxide or mixture thereof. A prepreg is produced by the above, and the fiber-reinforced ceramics are manufactured from this prepreg using the same curing and firing operations and heating atmosphere as described above (see Japanese Patent Publication No. 3-77138).

At first glance, their method seems to be similar to that of carbon fiber / epoxy prepreg, but the prepreg does not have effective tackiness, so that it is suitable for manufacturing products of curved shape or complicated shape. Handling is difficult and layer-to-layer peeling is likely to occur. In addition, since the flow is large, it cannot be handled unless it is partially cured, and therefore, three-stage curing operation including post-curing is required until complete curing, which requires time and labor for manufacturing. Is a drawback. In addition, the fact that the firing atmosphere is limited to the inert atmosphere or the vacuum obviously brings about manufacturing restrictions and cost increase.

HAN, Jong, Hoon disclose ceramic binder compositions having tack and drape properties. The composition comprises a polymer such as polymethylmethacrylate, a monomer such as trimethylolpropane trimethacrylate, a peroxide such as dicumyl peroxide and a solvent such as acetone. After compounding an inorganic fiber such as alumina fiber in a slurry liquid in which this binder composition and a ceramic component such as alumina are mixed, they are further cured at 149 to 170 ° C., and at a temperature of 480 ° C. or less. A method for producing a fiber-reinforced ceramic is disclosed, in which the binder is removed by firing and the ceramic component is sintered at 500 to 2,500 ° C. (see WO92 / 22509).

This method is based on the cross-linking agent / co-crosslinking agent system (Tama Matsumoto, "Rubber and organic peroxide vulcanization and co-crosslinking) conventionally used in the industry for vulcanizing rubber or crosslinking organic polymers. Agent "issued October 10, 1977, see Taiseisha Co., Ltd.)
Is used as it is as a binder for ceramic particles. This method is expected to have good shapeability because it has tackiness and drape unlike the ceramic precursor binder. However, in that this binder is composed entirely of organic matter,
It is no different from the polymer binder used in the conventional slurry impregnation method. Therefore, after debinding by thermal decomposition,
The bonding force between the ceramic particles drops sharply, and it is difficult to obtain fiber-reinforced ceramics having good mechanical strength unless the high-temperature high-pressure sintering method used in the conventional slurry impregnation method is used.

As described above, the conventional method for manufacturing a reinforced ceramic molded body has the following problems.

That is, (1) it takes a high temperature to sinter, (2) it takes a long time to manufacture, (3) it is difficult to perform firing at normal pressure and free standing, (4).
Difficult to manufacture products with complicated shape, (5) Mandatory use of expensive inert gas, (6) Large shrinkage and strengthening of matrix material during heating for ceramization Due to the large difference in dimensional change between the fiber and the matrix material during heating, many cracks are generated in the fired body.

All of these problems are disadvantageous for industrial production and commercialization of products.
These are the main causes that have hindered the spread of ceramic composite materials.

An object of the present invention is to use a ceramic composite material which solves the above-mentioned problems, and is made of a material capable of suppressing generation of toxic gas during combustion as much as possible and suppressing combustion of the material as much as possible. To provide vehicles. An object of the present invention is to use a ceramic composite material that solves the above problems, to further suppress the generation of toxic gas during combustion as much as possible, and to suppress the combustion of the material as much as possible. To provide a laminated structure suitable as. The purpose of this invention is
An object of the present invention is to provide an interior product and a panel that use a ceramic composite material that solves the above-mentioned problems, and further suppress the generation of toxic gas during combustion as much as possible and suppress the combustion of the material as much as possible. An object of the present invention is to provide a building that can be constructed using a material that suppresses the generation of toxic gas during combustion as much as possible and the combustion of the material as much as possible.

[0042]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the inventors of the present invention diligently studied and paid attention to the use of an inorganic long fiber reinforced ceramic material for at least one of an inner wall and a floor material of a vehicle. . As an example of the inorganic long fiber reinforced ceramic material, BLACKGLAS (trade name) described later and a ceramic material developed by the present inventors can be mentioned.

The ceramic material developed by the present inventors is produced by using a prepreg obtained by impregnating or heat infiltrating a specific matrix composition into a tow of inorganic fibers or a product of inorganic fibers. This prepreg has the advantages of tackiness, drapeability, and long out time equivalent to those of a prepreg for an epoxy resin composite. Here, as the matrix composition, a composition containing the components (A) to (E) in the present invention and a solvent and an additive which are optionally contained can be mentioned.

The prepreg can be used to produce a laminate having a complicated shape, and by heat-pressing under substantially the same conditions as the prepreg for the epoxy resin composite, the prepreg is firmly bonded to the matrix composition. It can be converted into a fiber-reinforced cured product having a good cross-linking structure and good bondability between the fiber and the matrix. This cured product has higher heat resistance than the fiber-reinforced epoxy resin composite material which is widely used at present, and has practicability itself. From this cured body, it is possible to produce a fiber-reinforced ceramic fired body by atmospheric pressure firing under unrestrained conditions in air, which is very easy to carry out industrially.
There is almost no shrinkage during firing, and no change in shape occurs. As used herein, heating under non-restraining conditions means heating and baking the cured product in a free-standing state without taking measures to prevent deformation, such as fixing it with a mold or pressing it with a press. Means that.

The fired body is further impregnated with a liquid containing at least one of the components constituting the matrix composition and re-fired, whereby voids generated during firing can be filled and the strength can be further improved. . In this way, fiber-reinforced ceramic fired body products having various shapes can be easily manufactured. This product is used for heat-resistant structural members and heat shield members for aircraft and space vehicles, jet engines, rocket engines, gas turbines. Heat-resistant and heat-shielding members such as engines, turbine blades, space equipment, heater or burner members, molding jigs, tools, or high-temperature furnace members such as furnace walls, furnace core tube protection tubes, reactor vessels, etc. Can be used for

The object of the present invention has been completed based on the above findings.

That is, the invention according to claim 1 is a vehicle provided with an inner wall material, wherein at least one of the inner wall material and the floor material is made of an inorganic long fiber reinforced ceramic material. In the invention according to claim 2, the inorganic long fiber reinforced ceramic material comprises ceramic long fibers, a metal oxide, an organic polymer and / or
Alternatively, the prepreg composed of a monomer to be an organic polymer and a curing agent therefor is molded and cured.
The invention according to claim 3, wherein the inorganic long fiber reinforced ceramic material comprises the following component (A):
Prepreg obtained by impregnating or heating and impregnating a tow of inorganic fibers or a product of inorganic fibers with a liquid or sheet of a matrix composition containing the components (B), (C), (D) and (E). The vehicle according to claim 1 or 2, which is obtained by molding, curing, and baking, wherein (A) component; fine powder of metal oxide having an average particle size of 1 μm or less; (B) component; double chain. A soluble siloxane polymer having a structure, (C) component; at least one ethylenically unsaturated double bond
Trifunctional silane compound in individual molecule, (D) component; organic peroxide, (E) component; at least 2 ethylenically unsaturated double bonds
In the invention according to claim 4, the amount of the component (A) in the matrix composition is 350 to 750 parts by weight, and the amount of the component (B) is 80. -170 parts by weight, the amount of the component (C) is 25 to 125 parts by weight, the amount of the component (D) is 1 to 4 parts by weight, and the amount of the component (E) is 25 to 125 parts by weight. The invention according to claim 5 is the vehicle according to claim 3, wherein the component (A) is an oxide or a composite oxide containing at least one selected from silica, alumina, and titanium oxide. The component (B) is a polysilsesquioxane, the component (C) is a γ- (meth) acryloxyalkyltrialkoxysilane, and the component (D) has a half-life of 10 hours. Peracid whose temperature is 110 ° C or higher It is those, the (E)
The component is a di (meth) acrylate of a polyhydric alcohol and / or a tri (meth) acrylate of a polyhydric alcohol, and the inorganic fiber includes glass fiber, alumina fiber, silica fiber, tyranno fiber, and alumina and / or silica. The vehicle according to claim 3 or 4, which is at least one selected from the group consisting of oxide-based inorganic fibers composed of various fibers as a main component, and the invention according to claim 6 is the inorganic long fiber. The reinforced ceramic material is
The surface of which is coated with a glaze burned product.
The invention according to claim 7 is the vehicle according to any one of claims 5 to 6, and the invention according to claim 7 is the vehicle according to any one of claims 1 to 6, wherein the vehicle is an aircraft. A honeycomb laminated structure in which an inorganic long fiber reinforced ceramic material is laminated on both sides or one side of a honeycomb, and the invention according to claim 9 is characterized in that the inorganic long fiber reinforced ceramic material is the same as the claim 2 or the above. The honeycomb laminated structure according to claim 7, which is obtained by molding and curing the prepreg according to claim 3, and the invention according to claim 10 is characterized in that the inorganic long fiber reinforced ceramic material is the ceramic material. (A) component, (B) component, (C) component described in 3,
The inorganic composition tow or the inorganic fiber product is impregnated or heat-penetrated with a liquid or sheet material of the matrix composition containing the component (D) and the component (E) in the content ratio described in claim 4. The honeycomb laminated structure according to claim 9, which is obtained by molding and curing a prepreg obtained by the method. The invention according to claim 11 is characterized in that the component (A) is selected from silica, alumina, or titanium oxide. Which is an oxide or a composite oxide containing at least one of the above, wherein the component (B) is a polysilsesquioxane, and the component (C) is a γ- (meth) acryloxyalkyltrialkoxysilane. The component (D) is a peroxide whose temperature for obtaining a half-life of 10 hours is 110 ° C. or higher, and the component (E) is a di (meth) acrylate of a polyhydric alcohol and Or a tri (meth) acrylate of a polyhydric alcohol, wherein the inorganic fibers are glass fibers, alumina fibers, silica fibers, tyrano fibers, and oxide-based inorganic fibers composed of various fibers containing alumina and / or silica as a main component. The honeycomb laminated structure according to claim 9 or 10, which is at least one selected from the group consisting of: The invention according to claim 12, wherein the surface of the inorganic long fiber reinforced ceramic material is glazed. The honeycomb laminated structure according to any one of claims 9 to 11 which is coated with a material, and the invention according to claim 13 is characterized by comprising an inorganic long fiber reinforced ceramic material. It is an interior component, and the invention according to claim 14 is characterized in that the inorganic long fiber reinforced ceramic material is the prepreg according to claim 2 or 3 above. The interior component according to claim 13, which is obtained by molding and curing a rubber, and the invention according to claim 15 is characterized in that the inorganic long fiber reinforced ceramic material is the component (A) according to claim 3. ,
A liquid or sheet material of a matrix composition containing the component (B), the component (C), the component (D) and the component (E) in the content ratio according to claim 4, is a tow of inorganic fibers or The prepreg formed by impregnating or heat infiltrating an inorganic fiber product is molded and cured, and the interior article according to claim 14, wherein the component (A) is silica, An oxide or a composite oxide containing at least one selected from alumina and titanium oxide, wherein the component (B) is a polysilsesquioxane, and the component (C) is γ- (meth) acryloyl. Roxyalkyltrialkoxysilane, the component (D) is a peroxide whose temperature for obtaining a half-life of 10 hours is 110 ° C. or higher, and the component (E) is a di (meta) of a polyhydric alcohol. ) An oxide of tri (meth) acrylate of rate and / or polyhydric alcohol, wherein the inorganic fibers are glass fibers, alumina fibers, silica fibers, tyranno fibers, and various fibers containing alumina and / or silica as a main component. The interior component according to claim 13 or 14, which is at least one member selected from the group consisting of inorganic fibers, and the invention according to claim 17, wherein the surface of the inorganic long fiber-reinforced ceramic material is a glaze. The interior article according to any one of claims 13 to 16 which is covered with a fired product, and the invention according to claim 18 is characterized by comprising an inorganic long fiber reinforced ceramic material. Therefore, the invention according to claim 19 is
19. The panel according to claim 18, wherein the inorganic long fiber reinforced ceramic material is formed by curing the prepreg according to claim 2 or 3, and curing the prepreg.
In the invention described in 0, the inorganic long fiber reinforced ceramic material is the component (A), the component (B) according to claim 3,
A liquid or sheet material of a matrix composition containing the component (C), the component (D) and the component (E) in the content ratios according to claim 4 is used as a tow of inorganic fibers or a product of inorganic fibers. The panel according to claim 19, which is obtained by molding and curing a prepreg that is impregnated or heat infiltrated, and the invention according to claim 21 is characterized in that the component (A) is silica, alumina, or titanium oxide. An oxide or a composite oxide containing at least one selected, the component (B) is a polysilsesquioxane, and the component (C) is a γ- (meth) acryloxyalkyltrialkoxysilane. The component (D) is a peroxide having a temperature of 110 ° C. or higher for obtaining a half-life of 10 hours, and the component (E) is a poly (alcohol) di (meth) acrylate and / Or a tri (meth) acrylate of a polyhydric alcohol, wherein the inorganic fibers are glass fibers, alumina fibers, silica fibers, tyranno fibers, and oxide-based inorganics composed of various fibers containing alumina and / or silica as a main component. The panel according to claim 19 or 20, wherein the panel is at least one selected from the group consisting of fibers, and the invention according to claim 22 is characterized in that the surface of the inorganic long fiber reinforced ceramic material is a glaze fired product. The panel according to any one of claims 18 to 21, which is covered, and the invention according to claim 23 is a building including an inner wall material, wherein the inner wall material uses an inorganic long fiber reinforced ceramic material. A building characterized by being made.

The invention according to claim 24 is the building according to claim 24, wherein the inorganic long fiber reinforced ceramic material is obtained by molding and curing the prepreg according to claim 2 or claim 3. The invention according to claim 25, wherein the inorganic long fiber reinforced ceramic material is the component (A), the component (B), the component (C) according to claim 3,
The inorganic composition tow or the inorganic fiber product is impregnated or heat-penetrated with a liquid or sheet material of the matrix composition containing the component (D) and the component (E) in the content ratio described in claim 4. 25. The building according to claim 24, which is obtained by molding and curing a prepreg obtained by the method. The invention according to claim 26 is characterized in that the component (A) is at least selected from silica, alumina, or titanium oxide. An oxide or a complex oxide containing one kind, wherein the component (B) is a polysilsesquioxane, and the component (C) is
γ- (meth) acryloxyalkyltrialkoxysilane, the component (D) is a peroxide whose temperature for obtaining a half-life of 10 hours is 110 ° C. or higher, and the component (E) is abundant. A di (meth) acrylate of a polyhydric alcohol and / or a tri (meth) acrylate of a polyhydric alcohol, wherein the inorganic fiber is mainly composed of glass fiber, alumina fiber, silica fiber, tyranno fiber, and alumina and / or silica. The interior article according to claim 24 or 25, which is at least one selected from the group consisting of oxide-based inorganic fibers consisting of various fibers
A twenty-seventh aspect of the present invention is the building according to any one of the twenty-second to twenty-sixth aspects, wherein the surface of the inorganic long fiber-reinforced ceramic material is coated with a glaze-fired material.

The present invention will be described in detail below.

-Vehicle- The vehicle of the present invention has at least an inner wall material made of an inorganic long fiber reinforced ceramic material, for example, a ceramic long fiber reinforced ceramic material.

The vehicle in the present invention refers to a general vehicle in which an occupant is on board and needs to protect the occupant from fire. Specific examples include passenger planes, cargo planes, transport planes, small planes, heliopters, and land and land vehicles. Amphibious boats, aircraft such as fighters, space shuttles, space vehicles such as manned rockets and spacecraft, trains,
And rail cars such as trains, buses, trucks, passenger cars,
Further, there may be mentioned automobiles such as special vehicles, passenger ships, cargo ships, tankers, sightseeing boats, hydrofoil ships, submarines, and ship ships such as submersibles.

The inner wall material in the vehicle is not particularly limited as long as it is a wall material that needs to protect the occupant from a fire. For example, a structural material forming a space surrounding the occupant, a space where a fire may occur, and the like. Examples thereof include a structural material that isolates a space where an occupant exists, and a structural material that surrounds a space where a fire may occur in order to protect the occupant from a fire.

As the space surrounding the occupant, for example,
Passenger cabin, crew deck, toilet, cockpit,
A cooking room (galley) or the like can be given, and a cargo room or the like can be given as a space in which a fire may occur.

Examples of the inner wall material include structural materials such as a wall, a ceiling, an opening / closing door for storage, an entrance / exit door, and a floor material in a space where an occupant exists or where a fire may occur. be able to. Although the floor material and the door may not be generally referred to as a wall body, in this specification, the inner wall material in the present invention is understood as a broad concept including a structural material constituting the floor material and the door. It

FIG. 1 shows the manner in which this inner wall material is used. This inner wall material is used, for example, in the passenger cabin 2
It is used as an inner wall 3, a floor material 5 that separates the passenger compartment 2 from the cargo compartment 4, a ceiling material 6 of the passenger compartment 2, and the like.

The inner wall material is a structural material having an inorganic long fiber reinforced ceramic material molded into a predetermined shape such as a plate shape, a curved plate shape, or a cylindrical shape, and is used for a wall body, a floor body, a ceiling body, or the like. A member that can be fixed to the surface by an appropriate fixing means such as an adhesive, screwing, nailing, or the like is included.

—Building— The building of the present invention comprises an inner wall material (in which the term is used to include flooring) using an inorganic long fiber reinforced ceramic material, particularly a ceramic long fiber reinforced ceramic material.

As shown in FIG. 7, the building 28 is erected at a vertically standing wall body 29, a floor material 30 laid between the wall bodies 29, and an upper end portion of the wall body 29. A ceiling member 32 attached to the lower surface of the beam member 31, a roof member 3 attached to a slant member 33 supported by the upper end of the wall body 29 and other portions.
Have 4. The wall body 29, the floor material 30, the ceiling material 32, and the roof material 34 can be formed of an inorganic long fiber reinforced ceramic material, particularly a ceramic long fiber reinforced ceramic material, and can be formed of the above-mentioned honeycomb laminated structure. .

-Interior Product- The interior product of the present invention comprises an inorganic long fiber reinforced ceramic material.

The interior parts of the present invention include various kinds of interior parts, such as walls, existing in the space where the passengers and the like are present, in addition to the wall material and the ceiling material which form the space where the people and the like are present. Lining material, floor lining material, ceiling lining material,
Baggage storage shelves, various instrument panel surfaces, chairs, desks, window frames, door frames, wall surface materials, ceiling surface materials, floor surface materials, pillars, ribs, dashboards, cable storage tubes, fixed boards for various members, etc. Can be mentioned. In short, the interior parts of the present invention are made of materials that exist in the space where the personnel exist, live or are active, and the presence of the personnel in order to effectively prevent the fire from spreading to the space where the personnel exist. Includes materials that are present in spaces where fire protection is required, with or without fire.

The interior part may have a structure in which the surface is made of an inorganic long fiber reinforced ceramic material. As a preferred structure, both surfaces are formed of an inorganic long fiber reinforced ceramic material, and the inside is a sheet, a film, a plate of a flame-retardant resin or a flame-retardant resin composition and / or a non-combustible resin or a non-combustible resin composition. It is made of foam.

There is no particular limitation on the form of the interior product. The shape of the inorganic long fiber reinforced ceramic material can be determined so as to have a shape according to the original shape of the interior component.

An example of a structure suitable for interior parts is shown in the drawings.

As shown in FIG. 2, this laminated structure 7 is
A flame-retardant resin sheet 9 is laminated on both sides of a sheet 8 formed of a heat-resistant resin composition, and an inorganic long fiber reinforced ceramic material layer 11 is laminated on the flame-retardant resin sheet 9 with an adhesive 10.
Are formed.

This flame-retardant resin composition comprises, for example, an inorganic fiber and a heat resistant resin. As the inorganic fibers, glass fibers, alumina fibers, silica fibers, tyranno fibers or oxide-based inorganic fibers made of various fibers containing alumina and / or silica as a main component, and carbon fibers may be used in some cases. it can.

The heat-resistant resin used in this flame-retardant resin composition is phenol resin, polyphenylene sulfide, polysulfone, polyether sulfone, wholly aromatic polyester, amorphous polyarylate, polyether ether ketone, polyimide. , Epoxy resin and the like. Preferred heat resistant resins include super engineering plastics such as phenolic resins and polyphenylene sulfide.

The flame-retardant resin used in this flame-retardant resin composition may be a thermoplastic resin containing a halogen atom, and preferable specific examples thereof include polyvinyl fluoride and polyfluorinated ethylene propylene copolymer. , Polyvinylidene fluoride and the like can be mentioned.

The inorganic long fiber reinforced ceramic material will be described later.

As the adhesive, an ordinary adhesive called a structural adhesive, such as an epoxy adhesive or a cyanoacrylate adhesive, can be used. An epoxy adhesive or the like can be given as an adhesive suitable for forming this laminated structure.

The thickness of the sheet formed of the heat-resistant resin composition, the flame-retardant resin sheet, and the inorganic long-fiber-reinforced ceramic material depends on what kind of inner wall material and interior product the laminated structure is used for. Can be appropriately determined according to

In this laminated structure, it is preferable that the surface of the inorganic long fiber reinforced ceramic material is coated with a sintered product of glaze. When the sintered product of the glaze is coated on the surface of the inorganic long fiber-reinforced ceramic material, the laminated structure can be made gas impermeable. Therefore, if an inner wall material or interior parts are formed with this laminated structure having a sintered product of glaze on the surface, no toxic gas in the event of a fire will permeate this laminated structure, thus ensuring the safety of passengers. be able to. In particular, in this laminated structure coated with a sintered product of this glaze, if the space where the occupant is present is surrounded, it is possible to prevent the toxic gas from entering the space when a fire occurs, or The invasion of toxic gas can be delayed.

As the glaze, for example, "polysilazane"
"Cosmo Coat", a perhydropolysilazane that can be easily obtained commercially as a (brand name) (brand name)
Etc. can be mentioned.

—Honeycomb Laminated Structure— The honeycomb laminated structure of the present invention can be used for the interior parts and panels of the present invention.

The honeycomb laminated structure may have various structures as long as it has a structure in which the inorganic long fiber reinforced ceramic material is laminated on both surfaces or one surface of the honeycomb laminated structure.

FIG. 3 shows a preferred embodiment of this honeycomb laminated structure. As shown in FIG. 3, in this honeycomb laminated structure 12, a sheet 14 made of a flame-retardant resin composition is laminated on both surfaces of a honeycomb 13, and a flame-retardant resin sheet 15 is laminated on the surface of the sheet. An inorganic long fiber reinforced ceramic material 17 is laminated on the surface of the flame-retardant resin sheet 15 with an adhesive 16 interposed therebetween.

The honeycomb material is not particularly limited as long as it has a honeycomb core. Examples of the honeycomb include a structure using a metal honeycomb formed of a metal such as aluminum, an aluminum alloy, and stainless steel, or a structure using a non-metal honeycomb formed of a resin such as a flame-retardant resin or an engineering plastic. be able to.

In order to further improve the flame retardancy of the honeycomb laminated structure, it is preferable to form the honeycomb with a metal honeycomb, and to reduce the weight and increase the rigidity, the honeycomb is formed with an aluminum honeycomb. preferable. Depending on the case, the honeycomb laminated structure may be formed of ceramics or an inorganic long fiber reinforced ceramic material.

In this honeycomb laminated structure, when a honeycomb and an inorganic long fiber reinforced ceramic material are combined, not only lightness, strength and impact absorption can be maintained, but also spread of fire from a fire occurrence site can be prevented. The combustion of the honeycomb laminated structure itself can be delayed.

This flame-retardant resin composition can be prepared, for example, by blending inorganic fibers and heat-resistant resin. As the inorganic fibers, glass fibers, alumina fibers, silica fibers, tyranno fibers or oxide-based inorganic fibers made of various fibers containing alumina and / or silica as a main component may be used, and carbon fibers may also be used in some cases. You can

The heat-resistant resin used in this flame-retardant resin composition includes phenol resin, polyphenylene sulfide, polysulfone, polyether sulfone, wholly aromatic polyester, amorphous polyarylate, polyether ether ketone, and polyimide. , Epoxy resin and the like. Preferred heat resistant resins include super engineering plastics such as phenolic resins and polyphenylene sulfide.

The flame-retardant resin used in the flame-retardant resin composition or the flame-retardant resin used in the flame-retardant resin sheet may be a thermoplastic resin containing a halogen atom. Specific examples thereof include polyvinyl fluoride, polyfluorinated ethylene propylene copolymer, polyvinylidene fluoride and the like.

The inorganic long fiber reinforced ceramic material will be described later.

Usual adhesives called structural adhesives such as epoxy adhesives and cyanoacrylate adhesives can be used as the adhesive.

The thickness of the honeycomb, the sheet formed of the heat-resistant resin composition, the flame-retardant resin sheet, and the inorganic long-fiber-reinforced ceramic material can be used for any inner wall material or interior product. It can be appropriately determined depending on whether it is used.

In this honeycomb laminated structure, it is preferable that the surface of the inorganic long fiber reinforced ceramic material is coated with a sintered product of glaze. When the surface of the inorganic long fiber reinforced ceramic material is coated with the sintered product of the glaze, the honeycomb laminated structure can be made gas impermeable. Therefore, when the inner wall material or interior parts are formed with this honeycomb laminated structure having the sintered product of glaze on the surface, the toxic gas at the time of a fire does not permeate this honeycomb laminated structure, and the safety of the passengers. Can be achieved. In particular, in this honeycomb laminated structure covered with a sintered product of this glaze, if the space where the occupant is present is surrounded, it is possible to prevent the toxic gas from entering the space when a fire occurs,
Alternatively, the invasion of toxic gas can be delayed.

Another mode of the honeycomb laminated structure is shown in the drawings. The honeycomb laminated structure 18 shown in FIG. 4 is a sheet 20 obtained by impregnating a honeycomb 19 with a thermosetting resin such as a phenol resin on both sides of a honeycomb 19 such as a glass fiber woven sheet, a knitted sheet or a non-woven sheet. Are stacked,
An inorganic long fiber reinforced ceramic material 21 is laminated on the surface of one of the sheets 20, and various patterns are printed or colored on the surface of the inorganic long fiber reinforced ceramic material 21 for the purpose of improving the appearance. The decorative sheet 22 is laminated, and the transparent protective sheet 23 is laminated on the surface of the decorative sheet 22. The honeycomb laminated structure may be used so that the transparent protective sheet 23 faces the indoor side.

The honeycomb laminated structure shown in FIG. 4 can be used as an inner wall material of an aircraft door as shown in FIG. 5, for example. The door 24 shown in FIG. 5 is a door attached to an entrance to and exit from the aircraft.

The honeycomb laminated structure shown in FIG. 4 can be used, for example, as shown in FIG. 6, for an opening / closing lid of a luggage storage rack installed in an aircraft.
As shown in FIG. 6, a luggage storage shelf 25 in an aircraft
Has an opening / closing lid 27 that covers the shelf body 26 and is formed so as to be openable and closable.

These honeycomb laminated structures can be used for the inner wall material or interior parts of the present invention in addition to the above. The honeycomb laminated structure is suitable as a floor material because of its strength. In addition, in the honeycomb laminated structure, the inner wall material or the interior component, the inorganic long fiber reinforced ceramic material is laminated on the surface of the space side where a heat source such as a fire exists.

-Panel-The panel of the present invention is formed by using an inorganic long fiber reinforced ceramic material. The panel of the present invention can be used for structural materials and interior parts that constitute vehicles and buildings. In the panel of the present invention, the honeycomb laminated structure is used by forming it into a curved surface or a plate so as to fit a predetermined structure. In particular, this panel can be preferably used as the outer surface of the fuselage of the aircraft or the inner wall of the interior. When this panel is used for forming the fuselage of an aircraft, the panel is mounted by inserting the end of this panel into the groove of the frame in a frame having an H-shaped cross section assembled to form the fuselage. , Or attached. Since the aircraft must keep the cabin airtight, the panel and the exterior material such as an aluminum plate or an alumina plate are hermetically sealed.

When this panel is mounted on the passenger side of an aircraft, and when the inorganic fiber reinforced ceramic material, especially the ceramic long fiber reinforced ceramic material, faces the passenger side, it means that an organic material is used for this panel. Therefore, even if smoke, gas, etc. are generated from this organic material during a fire, this inorganic long fiber reinforced ceramic material, especially ceramic long fiber reinforced ceramic material, effectively prevents the smoke, gas, etc. from leaking into the cabin. can do.

As a building panel, as shown in FIG. 8, a ceiling panel 35, a wall panel 36, and a floor panel 3 are provided.
7, base floor panel 38, door panel 39 and the like. As a panel used for other buildings,
Fireproof wall panels, fire wall panels, etc. in the kitchen can be mentioned.

These panels can be formed of the above-mentioned inorganic long fiber reinforced ceramic material, particularly ceramic long fiber reinforced ceramic material, and can also be formed of the above-mentioned honeycomb laminated structure.

—Inorganic Long Fiber Reinforced Ceramic Material— The inorganic long fiber reinforced ceramic material in the present invention includes (1) inorganic long fibers, metal oxides, organic polymers, and / or
Alternatively, a ceramic material obtained by molding and curing a prepreg composed of a monomer to be an organic polymer and its curing agent and a solvent (when a ceramic fiber is used as the inorganic fiber, this is referred to as a ceramic long fiber reinforced ceramic material). , And (2) Silicon Carboxide (SiC _x ), which is a silicon-based glass with a high refractive index.
_Oy ) and a thermosetting polymer precursor (monomer or low polymer), which is formed (coating, spinning, prepreg layup, etc.), and consists of silicon carbide and atom-dispersed carbon by firing. Mention may be made of ceramic composite materials.

As the ceramic composite material, “BLAC
KGLAS "(trade name, manufactured by Allied-Signal Inc).

The ceramic material, which is a ceramic long-fiber-reinforced ceramic material, can be manufactured by molding a prepreg, curing it, and then firing it, as described below.

The matrix composition used for producing the prepreg has the following components (A), (B),
It contains a component (C), a component (D) and a component (E).

Component (A); fine powder of metal oxide having an average particle size of 1 μm or less; component (B); soluble siloxane polymer having a double chain structure; component (C); ethylenically unsaturated double bond. At least 1
Trifunctional silane compound in individual molecule, (D) component; organic peroxide, (E) component; at least 2 ethylenically unsaturated double bonds
Radical-polymerizable monomer in individual molecule.

As the metal oxide as the component (A),
Single oxides such as silica, alumina, titanium oxide, lithium oxide, zinc oxide, tin oxide, calcium oxide, magnesium oxide, boron trioxide, zirconia, partially stabilized zirconia, vanadium pentoxide, barium oxide, yttria and ferrite. And complex oxides such as mullite, steatite, forsterite, cordierite, aluminum titanate, barium titanate, strontium titanate, potassium titanate and lead zirconate titanate. One of these may be used alone, or two or more thereof may be used in combination.

Among these metal oxides, preferable ones are
It is an oxide containing at least one selected from alumina, silica, or titanium oxide, or a composite oxide composed of these.

Suitable metal oxides have an average particle size of 1 μm.
m or less, particularly 0.5 μm or less. The fine powder of the metal oxide having such a fine particle diameter is mainly composed of the component (C),
It is included in the three-dimensional network structure formed by the component (D) and the component (E) in a state of being closely joined by the component (B), and therefore facilitates sintering. When metal oxide particles having an average particle size of more than 1 μm are used, it may not be possible to obtain a ceramic long-fiber-reinforced ceramic material having good strength.

The fine powder of metal oxide stored in the atmosphere has a hydroxyl group on at least a part of the surface thereof, and thus effectively functions for the bonding effect described later. In contrast,
Fine powders of metal nitrides, metal carbides, and the like do not always have the object of the present invention sufficiently achieved because they do not have sufficient hydroxyl groups on a part of their surfaces. Further, if it is attempted to manufacture a ceramic body from only the fine powder of the metal oxide, a high temperature and high pressure sintering operation is required, and the effect of the present invention cannot be achieved, and therefore the object of the present invention is achieved. I can't.

The soluble siloxane polymer having a double chain structure which is the component (B) may be a homopolymer or a copolymer. The component (B) acts as a binder for the metal oxide.

Generally, a so-called ladder-type organic polymer having a double-chain structure is superior in heat resistance to a linear organic polymer, is rigid, and is small in heat shrinkage. However, even if the organic polymer is a ladder type,
When heated above ℃, it is thermally decomposed or shrinks, and a large amount of gas is generated. Therefore, even if a prepreg fired body is manufactured using such a ladder-type organic polymer as a binder, the prepreg fired body There are many cracks and bubbles in the.

As a result of various studies on the binder of fine powder of metal oxide, the inventors have found that the siloxane homopolymer or siloxane copolymer having a double chain structure has a high second-order transition point (glass transition point), It has been found that it has a good bonding effect on oxides, and most of it is converted to a ceramic composition after pyrolysis, so that it is optimal as a binder for metal oxide fine particles in the present invention. The soluble siloxane polymer having a double chain structure in the present invention includes what is called an oligomer.

A raw material for preparing a siloxane polymer having a double-chain structure is represented by the chemical formula R'Si (OR) ₃
(In the formula, R is an alkyl group such as a methyl group or an ethyl group,
R'represents an aliphatic, alicyclic or aromatic substituent such as an alkyl group, a phenyl group, a vinyl group, a cyclopentyl group, a cyclohexyl group and a methacryloyl group. ).

As this trialkoxysilane, methyltriethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, octyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like can be mentioned.

The soluble siloxane polymer having a double-chain structure, which is the component (B), is described in, for example, JF Brown et at., J.
Prepared by hydrolyzing and condensing one or more trialkoxysilanes using an acid catalyst by a known method described in Polymer Sci., Part C No.1 p.83 (1963). be able to. These are also called polysilsesquiosans and are generally represented by the following chemical formula.

[0109]

[Chemical 1]

However, R ₁ represents a hydrogen atom or R in the chemical formula R′Si (OR) ₃ , and R ₂ and R ₃ represent R ′ in the chemical formula R′Si (OR) ₃ .

Examples of the polysilsesquioxane include polymethylsilsesquioxane, polyphenylsilsesquioxane, polyvinylmethylsilsesquioxane, polyphenylmethylsilsesquioxane, polyphenylpropylsilsesquioxane and polymethyl. Examples thereof include -n-hexylsilsesquioxane and polyphenylmethacryloxypropylsilsesquioxane.

Of these, polyphenylsilsesquioxane, polyphenylmethylsilsesquioxane and polyphenylethylsilsesquioxane are preferable. In the case of a copolymer, the molar ratio of phenyl group to methyl group or ethyl group (phenyl group / methyl group or ethyl group) is preferably 2/1 to 1/2. This is because these materials have a small heat shrinkage ratio during heating and are easy to manufacture.

The molecular weight of the siloxane polymer which is preferable as a binder is not particularly limited, but it is usually preferably 1,000 or more, and particularly preferably 1,500 or more.

For example, polyphenylsilsesquioxane is soluble in a solvent, can form a tough film from the solution, and has a glass transition point Tg of 300.
It is as high as 400 ° C., and therefore, thermal deformation during curing and firing can be suppressed to a minimum. Furthermore, this polymer does not undergo main chain scission even when heated to 900 ° C,
It is converted in high yield into a ceramic structure such as amorphous silicone oxycarbide (Si—C—O).

On the other hand, when the organic polymer is used as the binder, the organic polymer is thermally decomposed during the firing process under normal pressure,
The bonding force between metal oxides is lost and cracks occur.

As is clear from the above description, when the soluble siloxane polymer having a double-chain structure in the present invention is used as a binder, it shrinks little even when heated to a high temperature, and itself becomes a ceramic. ,
The shrinkage of the molded body is small. Therefore, the soluble siloxane polymer having this double chain structure is particularly advantageous for the firing operation under normal pressure and under unconstrained conditions. Here, the normal pressure includes a case where the operation of pressurizing or depressurizing is not intentionally applied.

In the present invention, of the soluble siloxane polymers having a double-chain structure, those having a silanol group or an alkoxy group at the molecular end are particularly advantageous. The soluble siloxane polymer having a silanol group or an alkoxy group at the molecular end has mutual affinity with the component (A) having a hydroxyl group on at least a part of its surface, that is, the fine particles of the metal oxide and the soluble siloxane polymer, Easily interdisperse. Further, they react with each other when heated and bond to each other, and when fired, they become an integrated ceramic.

However, even a soluble siloxane polymer having a double-chain structure with high thermal stability has a temperature of 1,000 ° C.
When heated to a high temperature in the vicinity, it shows a shrinkage of about 10%, which may cause a dimensional change in the fired body and cracks and voids. Therefore, the use of the component (B) alone achieves the object of the present invention. Can not do it.

In order to prevent the molded body from being deformed during firing at 1,200 ° C. even under normal pressure and under non-constrained conditions, the present prepreg cured body is preliminarily strengthened. It was confirmed that it was effective to form a simple three-dimensional network structure.

Component (C), which is necessary for forming a three-dimensional network structure, is a trifunctional silane compound having at least one ethylenically unsaturated double bond in its molecule, and component (D). Which is a radical-polymerizable monomer having at least two ethylenically unsaturated double bonds in the molecule, which is the organic peroxide and the component (E).

As already explained in the prior art, the crosslinking system by the combination of the rubber or polymer with the crosslinking agent (peroxide) and the co-crosslinking agent (reactive monomer) is already known, but the present invention The trifunctional silane compound having at least one ethylenically unsaturated double bond in the molecule, which is the component (C) as used in (4), the organic peroxide which is the component (D), and the component (E). There is no known crosslinking system in combination with a radically polymerizable monomer having at least two ethylenically unsaturated double bonds in the molecule.

The silane coupling agent is a compound having in its molecule a reactive group that chemically bonds with an inorganic substance such as a methoxy group and a reactive group that chemically bonds with an organic substance such as a resin such as a vinyl group or an amino group. It is widely used to improve the adhesion between a substance and an organic substance such as a resin and increase the strength of a composite. The silane coupling agent is usually used in either or both of a method of preliminarily treating the surface of an inorganic substance and a method of mixing with a resin.

In the present invention, the mutual affinity with the components (A) and (B) which are ceramics or ceramic precursor components and the component (E) which is an organic substance is increased,
It is necessary to have the action and effect of facilitating the formation of a strong network structure in the matrix and enhancing the bondability between the matrix substance and the inorganic fiber.

All known silane coupling agents cannot be used to achieve such action or effect. In the ceramic material as the ceramic long-fiber-reinforced ceramic material according to the present invention, a trifunctional silane compound having at least one ethylenically unsaturated double bond in the molecule is used as the component (C). The component (C) is easily bonded to the molecular end of the soluble siloxane polymer having a double-chain structure, which is the component (B), and the fine particles of the metal oxide. These bonds are generated by dehydration condensation of hydroxyl groups during heating. Further, since the trifunctional silane compound as the component (C) easily reacts with the surface hydroxyl groups of the inorganic fiber, the bondability between the matrix composition and the inorganic fiber can be enhanced. Therefore, in this respect, rather than nitride-based inorganic fibers and carbide-based inorganic fibers,
Oxide-based inorganic fibers are preferred. Furthermore, the ethylenically unsaturated double bond contained in the component (C) reacts with the radical catalyst as the component (D) and is incorporated into the network structure.

As the trifunctional silane compound having at least one ethylenically unsaturated double bond in the molecule, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyl Examples thereof include trimethoxysilane and γ-methacryloxypropyltriethoxysilane. Of these, γ-methacryloxyalkyltrialkoxysilane is preferable, and γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane are particularly preferable.

A cross-linking agent is required to form a network structure in a hardened body which is a precursor of a ceramic long-fiber-reinforced ceramic material. In this invention, the organic peroxide which is the component (D) is effective as a crosslinking agent.

In order to obtain the ceramic long-fiber-reinforced ceramic material, it is not preferable that the organic peroxide be decomposed to generate radicals during the work before curing in order to effectively act the organic peroxide. An organic peroxide having a temperature of 110 ° C. or higher for obtaining the desired period is preferable.

Examples of such organic peroxides include dicumyl peroxide, t-butylcumyl peroxide,
Di-t-butyl peroxide, α, α-bis (t-butylperoxyisopropyl) benzene, di-t-butylperoxydiisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexin-
3,1,1-bis (t-butylperoxy) -3,3
Examples thereof include 5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, and 2,2-bis (t-butylperoxy) octane.

The matrix composition for obtaining the ceramic long-fiber-reinforced ceramic material has at least an ethylenically unsaturated double bond as the component (E) in addition to the organic peroxide as a cross-linking agent as the component (D). It contains two, preferably three, radically polymerizable monomers. The component (E), as a co-crosslinking agent, contributes to the formation of a stronger three-dimensional network structure by curing. The matrix composition containing the component (E) contains fine particles of a metal oxide, and changes into a network structure having an effective and sufficient chain length that is not deformed by heating.

Examples of the component (E) include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene glycol diitaconate, tetramethylene glycol diitaconate, ethylene glycol dicrotonate and ethylene glycol di. Examples thereof include maleate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like. In the above example,
The expression (meth) acrylate refers to both acrylates and methacrylates.

Among these, radical polymerization is excellent,
From the viewpoint of giving an effective chain length and excellent tackiness to the prepreg as described later, di (meth) acrylate of polyhydric alcohol and / or tri (meth) acrylate of polyhydric alcohol such as trimethylolpropane trichloride. (Meth) acrylate is preferred.

Each component constituting the above matrix composition is dissolved or dispersed in an organic solvent.

The solvent may be appropriately selected depending on the kind of each constituent and the mixing ratio thereof. The solvent preferably used in the present invention is selected from alcohols, aromatic hydrocarbons, alkanes, ketones, nitriles, esters, glycol esters and the like. It is preferred that the solvent be completely removed prior to curing, and thus a solvent such as low boiling acetone is preferred, but not necessarily limited thereto. The solvent may be used alone or two or more of them may be used in combination.

In order to obtain a ceramic long-fiber-reinforced ceramic material, the components (A) to (E) are added to the solvent as uniformly as possible so as to give a dense structure to the ceramic matrix body after firing. It is preferably dissolved or dispersed. For that purpose, the component (B),
Component (C), component (D) and component (E) are each dissolved in a solvent with stirring, component (A) is added to the resulting solution, and stirring is continued until each component is uniformly dispersed. Although the method may be adopted, this good ceramic long-fiber ceramic material is also obtained by adopting the method of adding all of the components (A) to (E) to the solvent at the same time and stirring them sufficiently. be able to. Further, a minute amount of a dispersion stabilizer such as a known surfactant may be added. Further, addition of known additives is not prevented as long as the properties of the matrix composition are not impaired.

The ratio of each component in the matrix composition is
It is appropriately selected depending on the type of each component and the performance of the prepreg cured product or prepreg fired product that is combined with each component. In many cases, the matrix composition has the following component ratios.

That is, the compounding amount of the component (A) is 350-
750 parts by weight, preferably 450-650 parts by weight,
The compounding amount of the component (B) is 80 to 170 parts by weight, preferably 100 to 150 parts by weight, and the compounding amount of the component (C) is 25 to 1 part.
25 parts by weight, preferably 50 to 100 parts by weight, the amount of the component (D) is 1 to 4 parts by weight, preferably 1.5 to 3 parts by weight, and the amount of the component (E) is 25 to 125 parts by weight, It is preferably 50 to 100 parts by weight.

The tackiness of the prepreg is adjusted by the amount of the component (E) in combination with other components. Therefore, the role of the component (E) is not limited to the formation of the network structure, and plays an important role in the formation of tackiness which is an important effect of the present invention.

The matrix composition for obtaining the ceramic long fiber reinforced ceramic material is used while having a solvent as described later, or is used as a sheet by removing the solvent.

The prepreg for obtaining the ceramic long-fiber-reinforced ceramic material can be produced by impregnating or heating and impregnating the liquid or sheet of the matrix composition into the inorganic fiber tow or its product. Further, the prepreg for obtaining the ceramic long fiber reinforced ceramic material is 1 cm in size with the matrix composition.
It can also be obtained by mixing with the above cut fibers. The ceramic long-fiber-reinforced ceramic material having a predetermined shape can be obtained by molding a prepreg sheet or directly molding a mixture of the matrix composition and cut fibers of 1 cm or more.

The inorganic fiber may be heated to at least 500 ° C. or lower, preferably 1,000 ° C. or lower, and more preferably 1,200 ° C. or lower in either an inert atmosphere or an oxidizing atmosphere such as air. It is preferable to keep the strength for practical use. Nitride-based inorganic fibers, carbide-based inorganic fibers, oxide-based inorganic fibers, and carbon fibers can be mentioned as those satisfying such conditions. These inorganic fibers have sufficient heat resistance and reinforcing effect required in the present invention.

Preferred inorganic fibers are glass fibers,
Alumina fiber, silica fiber, Tyranno fiber (Si-Ti-
C-O), and oxide-based inorganic fibers composed of various fibers containing alumina and / or silica as a main component. Although the strength of glass fiber decreases at high temperature, its strength at room temperature is higher than that of other oxide-based inorganic fibers.
Even at a temperature around 00 ° C., it is possible to obtain a ceramic long-fiber-reinforced ceramic material having sufficient strength to achieve the object of the present invention. Although carbon fiber can be used as the inorganic fiber, the heat resistance of carbon fiber in the presence of air is 900 ° C or higher, and depending on the fiber, it is not so excellent at 800 ° C or higher. It is preferable to cover with a material that does not easily diffuse air, such as glass. Further, it is preferable to use without firing or to lower the firing temperature. Otherwise, ceramic filaments are superior to carbon fibers.

When a commercially available product is used as the inorganic fiber,
It is preferable to remove the adhering sizing agent before use.

As the inorganic fibers, filaments are usually used, but staples may be used as long as they have a length of 1 cm or more.

The feature of the fiber reinforced ceramics is that the fracture process is controlled by the frictional force between the interface between the fiber and the matrix, and the fiber bears the load. Therefore, in the case of the fiber-reinforced ceramics, unlike the fiber-reinforced plastics and the fiber-reinforced metal, the bonding force between the interface between the fiber and the matrix is not too strong, and the fiber pull-out (Pu
It is said that it is particularly important that the control is performed to the extent that it can guarantee the (ll-out) (Koichi Niihara, NIKKEI MECHANIC
AL 1989 12.11 p114). This means that even if it is desired that the fibers and the matrix composition are sufficiently bonded in the prepreg and the cured prepreg,
In the prepreg fired body, it is shown that it is preferable that the fiber and the matrix are rather weakly bonded.

Carbon and boron nitride are known as fiber surface coating agents capable of forming such an interface. In air, carbon is said to oxidize above about 450 ° C. and boron nitride above about 900 ° C., thereby providing a weak interface between the fiber and the matrix.
It is effective to apply such a known fiber surface coating to the inorganic fibers used in the present invention in order to further improve the mechanical properties of the fired prepreg.

The inorganic fiber is used as a tow aligning material, or as a knitted or woven form.

A prepreg for obtaining an inorganic long fiber reinforced ceramic material, for example, a ceramic long fiber reinforced ceramic material, is a solvent method (also referred to as a wet method) employed in the production of conventional epoxy resin prepreg, or a hot method. It can be produced by using a method similar to the melt method (also referred to as a dry method).

In the method according to the solvent method, the inorganic fiber tow or its product is dipped in the liquid of the matrix composition,
After squeezing out the excess liquid, blowing hot air or passing it through a dryer to remove the solvent,
A prepreg is obtained.

Further, in the hot melt method, a sheet-like material having a predetermined basis weight (this term includes a film-like material as a concept) is formed from the liquid of the matrix composition, and the tow of inorganic fibers or the inorganic fibers is formed. By laminating the sheet-like material on one side or both sides of the product, or by alternately laminating the sheet-like material with a tow of inorganic fibers or a product of inorganic fibers, and heating the same to a temperature of 120 ° C. or less. A prepreg can be obtained by impregnating the matrix composition between the inorganic fibers while reducing the viscosity of the sheet material.

The prepreg thus obtained has tackiness and drapeability sufficient for forming a laminate, and outtime property sufficient for work.

This prepreg is flexible and has adhesiveness. Therefore, it is possible to sufficiently follow a variety of complicated shapes or structures. Furthermore, even if it is integrated with other materials, if the mating material has heat resistance, it will be integrated at the prepreg stage and then fired to remove the adhesive that causes gas and smoke at high temperatures. It can be molded into an interior product such as a panel or its surface material without using it.

Therefore, a panel obtained by laminating the inorganic long fiber reinforced ceramic material, particularly the ceramic long fiber reinforced ceramic material, and the honeycomb is suitable as a good inner wall material, a honeycomb structure and an interior article.

The prepreg thus manufactured is
After being formed into a predetermined shape required for the inner wall material and the interior material of the vehicle by a known method such as a laminating method or a filament winding method, a heating and pressing treatment, that is, a curing treatment is applied. It should be noted in the present invention that the curing reaction is sufficiently completed by the one-step curing, so that the two-step curing (including the pre-curing) and the three-step curing (including the pre-curing and the post-curing) are not required. That is. However, in some cases, these pre-curing and post-curing may be performed without any problem.

As preferable curing treatment conditions, heating temperature is 120 to 250 ° C. and pressure is 2 to 10 kg / c.
It can be pointed out that m ² is 10 to 60 minutes as the processing time.

The curing operation is performed in an autoclave after a vacuum bag or by using a hot press.

The former is advantageous for industrial production because it can manufacture complicated and large-sized products.

The obtained prepreg cured product has neither shrinkage nor surface cracks observed, and has almost no weight loss. Specifically, this cured product has, for example, 25 to
It has a bending strength of about 50 kg / mm ² and hardly shrinks even when heated to 1,000 ° C. in air and under normal pressure.

As described above, the reason why the prepreg cured product hardly causes heat shrinkage is that the fine particles of the metal oxide maintain a high density and sufficient contact state in the strong three-dimensional network structure formed by the curing. It is considered that this is because the filler is filled and the inorganic fiber and the matrix maintain a good bonding state and peeling or separation does not occur.

The obtained prepreg cured product is, if necessary, at 500 to 1,200 ° C., preferably 600 to 1,0.
By heating to a temperature between 00 ° C., it is converted into a fired body reinforced with inorganic fibers. As the heating temperature,
Although the temperature may exceed 1,200 ° C,
Heating to a too high temperature may reduce the strength of the inorganic fiber, which is not preferable. Further, by heating at a temperature rising rate of 5 ° C./min or less, preferably 2 ° C./min or less up to 500 ° C. at the initial stage of temperature raising, particularly in the temperature range of 100 to 450 ° C., the generation of deformation and cracks is effective. Can be prevented. Under such heating conditions, this prepreg cured product can be heated under normal pressure and under unrestrained conditions. In this way, the prepreg cured product heated to a predetermined temperature is held at that temperature for preferably 10 minutes or more, and then cooled according to a conventional method.

The heating atmosphere may be an oxidizing atmosphere such as air or an inert gas atmosphere. However, the prepreg fired body obtained in an inert atmosphere has a black color due to the carbon content remaining in the matrix without being released by thermal decomposition. When this prepreg fired body is refired in air, carbon content is released and it becomes white. Therefore, when the prepreg fired body is used as it is in the high temperature atmosphere in this inert atmosphere, the residual carbon content is oxidized and released as a gas body. Further, the prepreg fired body in the inert atmosphere tends to have lower strength than the prepreg fired body in the air.
From these points, it is possible to carry out firing in an inert atmosphere, but it cannot be said that it is necessarily advantageous in terms of the number of steps and performance as compared with firing in air.

One of the important effects of the present invention is that the firing operation can be carried out in air under normal pressure and under unconstrained conditions without deformation. by this,
It becomes possible to easily manufacture a large-sized ceramic component having a complicated shape.

In order to achieve this effect, the components of the matrix composition are (A) component, (B) component,
All of the five components, component (C), component (D) and component (E), are essential, and even if one component is lacking, the object of the present invention cannot be achieved. The prepreg fired body, which is the ceramic long-fiber-reinforced ceramic according to the present invention, can be sufficiently put to practical use as it is, but the performance can be further improved by the densification treatment shown below.

The prepreg cured product contains an organic content of 10 to 15%, though it depends on the mixing ratio of its constituent components. Some of this is incorporated into the ceramic composition, while the rest is released as a gas during firing, which creates fine voids in the fired body. The fine voids are the components (A) constituting the matrix composition ~
The prepreg fired body is immersed in a liquid containing the component (E) or a liquid containing at least the component (B), and
It can be filled by rebaking at a temperature of 1,200 ° C., preferably between 600 and 1,200 ° C. You may repeat this densification process. In the present invention, the densified prepreg fired body can also be suitably used as an inorganic long fiber reinforced ceramic material, for example, a ceramic long fiber reinforced ceramic material.

When the inorganic long fiber reinforced ceramic material thus obtained, for example, the ceramic long fiber reinforced ceramic material is laminated on another material, it is preferable to use a heat resistant inorganic adhesive for the lamination. The use of this heat-resistant inorganic adhesive also applies to the formation of the above-mentioned honeycomb laminated structure, interior parts, and inner wall material. When an inorganic long fiber reinforced ceramic material such as a ceramic long fiber reinforced ceramic material is laminated on another material, when an organic adhesive is used for the lamination, a phenol resin or the like is used rather than an epoxy adhesive. It is preferable to use the above-mentioned phenolic adhesive, particularly a phenolic adhesive containing a vinyl-modified phenol resin. Such a phenol-based adhesive is preferable because it has low exothermic property and smoke generation property upon combustion.

A laminated structure and a honeycomb laminated structure using the inorganic long fiber reinforced ceramic material including the prepreg fired body obtained as described above, the interior parts, and the panal have good heat resistance and are difficult. Has flammability,
It is suitable as a material to protect people from fire accidents.

-Evaluation method for fire-When inorganic long fiber reinforced ceramic materials, especially ceramic long fiber reinforced ceramic materials, are applied to inner wall materials and interior parts used for aircraft among vehicles, the fire protection required for aircraft materials can be obtained. The required value for can be met.

This required value is FAA Regulation 14 CFR C
h.1 (1-1-93 version) This is the standard evaluated by the test method described in Section 25.853, Part 1.

The required values in the above test method are (1) self-extinguishing property in vertical flame test, (2) average burn length not exceeding 6 inches, (3) flame The average burning time after removing the source does not exceed 15 seconds, and (4) the flame does not emit for an average of 3 seconds or more after dropping the Dripping from the sample.

The contents of this test method are as follows.

(A) Test atmosphere temperature: 70 ± 5. F Humidity: 50 ± 5% RH (b) Test execution conditions A combustion test is performed after the temperature and humidity have been reached and equilibrium has been reached, or after 24 hours have elapsed. The sample is left under the equilibrium state.

(C) Sample shape A flat plate is cut out from the product. Create a sample of the same shape. For sandwich panels, test with the same structure. The sample thickness shall not exceed the minimum product thickness.

(D) Fixing of sample Fix the four corners of the sample with the metal frame. The sample surface exposed to the flame should be at least 2 inches (width) x 12 inches (length). The sample surface exposed to the flame in the later-described 45-degree combustion test is 8 inches (width) × 8 (length).

(E) Number of Samples The number of samples is 3 or more. The average value of the test results for three or more samples is taken as the test result.

(F) Flame source A Bunsen burner or a Tirrill burner is used.
The inner diameter of the burner is 3/8 inch. The height of the flame is 1.
5 inches. As the flame temperature, the central temperature of the flame is 155
0. Let it be F. Temperature should be measured with a thermocouple or pyrometer.

(G) Test content (g-1) Vertical test A vertical burner flame is blown onto the vertical surface of a vertically standing sample. The distance between the tip of the burner and the vertical surface of the sample is 3/4 inch. The test time is 60 seconds.

(G-2) Horizontal test A burner flame is blown to the horizontal lower surface of the sample held horizontally. The distance between the tip of the burner and the lower horizontal surface of the sample is 3/4 inch. The test time is 15 seconds.

(G-3) 45 ° test A burner flame is blown onto the inclined lower surface of the sample inclined at 45 °. One-third of the flame hits the sample. The test time is 30 seconds.

[0178]

【Example】

(Example 1-Preparation of matrix composition I) Alumina powder (average particle size;
0.4 μm) 400 parts by weight, titanium oxide powder (average particle size 0.4 μm) 200 parts by weight, polyphenylmethylsilsesquioxane (molecular weight 2,300, phenyl / methyl ratio = 6/4) 125 parts by weight, γ -Methacryloxypropyltrimethoxysilane 40 parts by weight, trimethylolpropane trimethacrylate 25 parts by weight, 2,5-dimethyl-
2,5-di (t-butylperoxy) -hexyne-3
Add 2 parts by weight and 250 parts by weight of acetone, mix by rotating the ball mill for 1 hour, and dissolve uniformly,
A dispersed liquid matrix composition I was obtained.

Example 2-Preparation of Matrix Composition II
In a glass cylindrical container equipped with a stirrer, 125 parts by weight of polyphenylethylsilsesquioxane (molecular weight 1,700, phenyl / ethyl ratio = 5/5), 100 parts by weight of γ-methacryloxypropyltriethoxysilane, 30 parts by weight of trimethylolpropane triacrylate, 1.3 parts by weight of dicumyl peroxide and 250 parts by weight of acetone were added and stirred until a uniform solution was formed. 300 parts by weight of alumina powder (average particle size 0.4 μm) and 200 parts by weight of silica powder (average particle size 0.02 μm) were added to this solution with stirring, and the mixture was dispersed well by applying ultrasonic vibration to form a matrix composition. II was prepared.

Example 3-Preparation of Matrix Composition III By slowly stirring the matrix composition prepared by the method of Example I above, acetone in the matrix composition was added until the solution viscosity reached 300 poises. Evaporated. As a result, a dense matrix composition III having a good film forming ability was obtained.

Example 4-Preparation I of Prepreg The matrix composition I prepared in Example 1 was prepared by adding a fabric of alumina fibers (85% by weight of alumina, 15% by weight of silica) (Altex Cloth, SV-600-8H, (Sumitomo Chemical Co., Ltd.), the excess matrix was removed using a squeeze roll, the mixture was placed in a hot air circulation dryer at 80 ° C. for 5 minutes to evaporate acetone, and the matrix composition content was 60% by weight. An inorganic fiber reinforced prepreg was manufactured.

The tackiness, drapeability and out time of this prepreg were evaluated by a method similar to that of the conventional epoxy prepreg, and the results are shown in Table 1. As shown in Table 1, good results were obtained.

[0183]

[Table 1]

Example 5-Preparation of prepreg II Example 3 above
A film having a thickness of 0.15 mm was prepared from the matrix composition III prepared in Step 1 by a film coater. This film was attached to both sides of the same woven fabric of alumina fiber as used in Example 4 and impregnated through a hot roll at a temperature of 120 ° C. to prepare a prepreg having a matrix composition content of 50%. It was confirmed that this prepreg had tackiness, drapeability and outtime that passed the evaluation method shown in Example 4 above.

Example 6-Preparation of prepreg III A pre-defatted alumina fiber (85% by weight alumina, silica 1)
5% by weight) tow (Altex SV-10-1K, manufactured by Sumitomo Chemical Co., Ltd.) is immersed in the liquid matrix composition I prepared in Example 1 to impregnate the tow with the composition I, and the nozzle And squeeze it with a filament winder, and 1.5 on a drum with a diameter of 30 cm wrapped with release paper.
After winding the tow at a pitch of mm, it was cut and removed from the drum. This was placed in a hot air circulation type dryer at 80 ° C. for 5 minutes to evaporate acetone to produce a unidirectional prepreg having a matrix composition content of 50%. It was confirmed that this prepreg also had tackiness, drapeability and outtime that passed the evaluation method shown in Example 4.

Example 7-Preparation I of Prepreg Cured Product I A stack of 9 layers of the prepreg prepared in Example 6 was laminated in a vacuum bag by a conventional method, placed in an autoclave, and the pressure was raised to 7 kg / cm ² . The temperature was raised to 220 ° C. at a temperature rate of 2.5 ° C./min, the temperature was maintained for 30 minutes, and then the temperature was lowered at 4.5 ° C./min to manufacture a prepreg cured plate having a thickness of 3 mm. A test piece having a width of 4 mm and a length of 36 mm was cut out from this prepreg cured product, and a similar bending test was performed in the following examples in accordance with JIS R 1601.
The bending strength was kg / mm ² . In addition, the measured value shown below this example is an average value of five samples.

(Example 8--Preparation of cured prepreg II) Four layers of the prepreg prepared in Example 4 were laminated in the directions of 0 ° and 90 °, and were hot pressed at 200 ° C for 15 minutes to obtain 3.5 kg.
A prepreg cured product having a thickness of 2 mm was produced under the condition of / cm ² . The obtained prepreg cured product has good mechanical strength, shrinkage and the occurrence of surface cracks are not observed,
The weight loss was 0.7%. When the bending strength of this prepreg cured product was measured in the same manner as in Example 7,
It was 28.0 kg / mm ² .

(Example 9--Preparation of cured prepreg III)
Four layers of the prepreg manufactured in Example 5 were laminated in the directions of 0 ° and 90 °, and hot pressed at 150 ° C for 15 minutes at 3.5k.
A prepreg cured product having a thickness of 2 mm was produced under the condition of g / cm ² . The obtained prepreg cured product had good mechanical strength, no shrinkage or surface cracking was observed, and the weight loss was 0.6%. When the bending strength of this prepreg cured product was measured in the same manner as in Example 7, it was 32.3 kg / mm ² .

Example 10-Calcination I of Prepreg Cured Product I
The prepreg cured product produced in Example 7 was heated to 500 ° C. at a temperature rising rate of 1 ° C./min in air under normal pressure, and then heated to 1,000 ° C. at 2 ° C./min at that temperature. Firing was carried out by holding for a time to manufacture an alumina fiber reinforced ceramic laminate (prepreg fired body).

Almost no dimensional change was observed between the prepreg cured product and the obtained prepreg fired product. The weight was reduced by 7.3% as compared with that before firing.

--High Temperature Strength Test-- The results of high temperature bending test at 800 ° C. and 1,000 ° C. of this laminated plate are shown in Table 2. Bending test is J
It carried out according to ISR 1604. As shown in Table 2, it was recognized that the higher the temperature, the higher the strength. It is presumed that this is due to a decrease in the bondability between the fiber and the matrix due to an increase in temperature, an increase in the fiber pullout effect, and / or an increase in the elongation of the matrix.

[0192]

[Table 2]

--Heat Cycling Test-- With respect to this laminated plate, the room temperature bending strength in each cycle when the heat cycle was changed to 5, 10, 15, 20 times between room temperature and 1,000 ° C. It measured and obtained the result shown in Table 3. As shown in Table 3, no decrease in strength was observed in the thermal cycle between room temperature and 1000 ° C.

[0194]

[Table 3]

(Example 11--Calcination of cured prepreg II)
The prepreg cured product produced in Example 9 was heated to 800 ° C. at a heating rate of 1.5 ° C./min in air under normal pressure, and was held at that temperature for 1 hour for firing to obtain an alumina fiber reinforced ceramic. A laminate (prepreg fired body) was manufactured.
The dimensional shrinkage between the prepreg cured product and the prepreg fired product was 0.03% in the length direction and 0.8% in the thickness direction.

A high temperature strength test and a heat cycle test were conducted on this laminated plate by the method shown in Example 10, and Table 4
And, as shown in Table 5, the same tendency as shown in Tables 2 and 3 was observed.

[0197]

[Table 4]

[0198]

[Table 5]

Example 12-Densification Treatment I In a glass cylindrical container equipped with a stirrer, polyphenylmethylsilsesquioxane (molecular weight 1,700, phenyl / methyl ratio =
5/5) 125 parts by weight, 100 parts by weight of γ-methacryloxypropyltrimethoxysilane, 1.3 parts by weight of dicumyl peroxide and 300 parts by weight of N-vinylpyrrolidone were added and stirred until a uniform solution was formed. .

The alumina fiber reinforced ceramic laminate of Example 11 was immersed in the above solution placed in a glass cylindrical container, and then kept under reduced pressure until no bubbles were generated. Then, the reduced pressure was released, the laminate was taken out, the solution adhering to the surface was removed, and acetone was completely evaporated in a dryer at 80 ° C. This impregnated laminated plate was placed in an electric furnace, heated to 800 ° C. at a heating rate of 1 ° C./min in air, and held for 1 hour to manufacture a densified ceramic laminated plate. This sample was used as the first impregnated sample, and the same impregnation, drying, and firing operations were repeated.
Repeated three times. These are the second impregnated sample, the third
This was a sample impregnated once. The bending test results of each impregnated sample are shown in Table 6. It can be seen that the flexural strength of the laminate improved with the number of impregnations.

[0201]

[Table 6]

(Example 13--Densification treatment II) The alumina fiber-reinforced ceramic laminate of Example 11 was placed in a vacuum chamber, the inside was evacuated, and methylphenylvinylhydrogenpolysiloxane (H62C) preheated to 80 ° C. was used. , Wacker
-Chemie GmbH) was injected and left overnight. Then, the inside of the vacuum chamber was opened to atmospheric pressure, and then the laminate was taken out to remove the solution adhering to the surface. Then, the impregnated laminated plate was put into an electric furnace, heated to 800 ° C. at a heating rate of 1.5 ° C./min in air, and kept at that temperature for 1 hour. The mechanical properties of the laminate before and after densification are listed in Example 17, Table 11.

(Example 14--Densification treatment III) The alumina fiber-reinforced ceramic laminate of Example 10 was placed in a vacuum chamber, and a densified ceramic laminate was produced in the same manner as in Example 13.

This sample was used as the first impregnated sample, and the same operation was repeated twice to obtain the second impregnated sample. The bending test result of each impregnated sample is shown in Table 7.

[0205]

[Table 7]

(Example 15--Example in which inorganic fiber is glass fiber)
In a ball mill containing ceramic balls, 400 parts by weight of alumina powder (average particle size; 0.4 μm), 200 parts by weight of titanium oxide powder (average particle size; 0.4 μm), polyphenylsilsesquioxane (molecular weight: 1,700) ) 125 parts by weight, 50 parts by weight of γ-methacryloxypropyltrimethoxysilane, 50 parts by weight of trimethylolpropane triacrylate, 2 parts by weight of dicumyl peroxide and 250 parts by weight of methanol were added and mixed by rotating the ball mill for 1 hour. A homogeneously dissolved and dispersed matrix solution was obtained.

A glass fiber fabric (6781HT-38, manufactured by Hexel) was dipped in this matrix solution,
Excessive matrix solution was removed using a squeeze roll and put in a hot air circulation dryer at 80 ° C. for drying to prepare a prepreg having a matrix composition content of 65% by weight.

It was confirmed that this prepreg also had tackiness, draping property, and outtime property that passed the evaluation method shown in Example 4.

This prepreg is 8 degrees in the directions of 0 ° and 90 °.
The layered product was vacuum-bagd by an ordinary method and placed in an autoclave, the pressure was 5 kg / cm ² , and the heating rate was 2.5 ° C. /
After raising the temperature to 150 ° C. for 15 minutes and holding for 15 minutes, 4.5
The temperature was lowered at ° C / min to prepare a plate of a prepreg cured body having a thickness of 3 mm.

No shrinkage or surface cracking was observed in the obtained prepreg cured product, and the weight loss was 1.1%.

This prepreg cured product was heated to 400, 500, 600, 7 at a temperature rising rate of 1.5 ° C./min in air under normal pressure.
The temperature was raised to each temperature of 00 ° C., and the temperature was maintained for 1 hour.

[0212] The weight reduction rate was measured by the thermal analysis device TG / DTA3.
0 (manufactured by Seiko Denshi Kogyo Co., Ltd.) was measured under an air stream at a temperature rising rate of 1.5 ° C./min. In this case, 40
A temperature rising test was performed up to temperatures of 0, 500, 600, and 800 ° C. Table 8 shows the weight reduction rate and the bending strength of the fired laminate (pre-preg fired body). The weight reduction rate is shown as a value obtained from the cured laminate.

[0213]

[Table 8]

The weight reduction rate increased as the temperature increased, but reached a constant value at 600 ° C. Further, the color of the test piece after firing was still colored after the treatment at 500 ° C. for 1 hour, but became white at 600 ° C. or higher.

These results show that the organic components in the matrix or their decomposition products remain at 500 ° C. or lower,
It is shown that above 600 ° C., they are completely released and converted into a ceramic composition. The bending strength of the fired product of 600 ° C. or higher is lower than that of the fired product of 500 ° C. or lower, which is considered to be due to the generation of defects due to the release of organic components. It should be noted that a heat treatment time of 10 minutes or longer is sufficient at 600 ° C. to release the organic component and convert the preceramic component into a ceramic composition. The present results also suggest that even if the heat treatment is performed at a lower temperature for a long time, a firing temperature of at least 500 ° C. is required.

Although the glass fiber has a larger strength decrease with temperature rise than the ceramic fiber such as alumina fiber, its room temperature strength is much higher than that of the ceramic fiber. For example, in the case of S-glass fiber (manufactured by Owens Corning Fiberglass Co., Ltd.) or T-glass fiber (manufactured by Nitto Boseki Co., Ltd.), which holds a tensile strength of about 200 kg / mm ² . Therefore, the fact that the preceramic component in the present invention, that is, the component (B) and the component (C), can be made into a ceramic even by a heat treatment at 600 ° C. for a short time makes it possible to use glass fiber which is lower in heat resistance than the ceramic fiber but is inexpensive. It shows that.

(Example 16--Influence of firing atmosphere) Four layers of the prepreg produced in Example 4 were laminated and hot pressed under the conditions of Example 9 to obtain a length of 160 mm, a width of 160 mm, and a thickness of 2 mm.
After producing a cured laminate of, the plate was separated into two.
One was to raise the temperature in air to 800 ° C. at a temperature rising rate of 1 ° C./min and hold the temperature for 1 hour. The other one was fired in nitrogen under the same conditions. In each case, the densification treatment under normal pressure was performed once by the same method as in Example 13.

Table 9 shows the change in weight due to firing and densification treatment (the weight of the cured product is 100) and the bending test result of the densified product (by the method described in Example 7).

[0219]

[Table 9]

The reason that the change in weight is smaller than that in the case of baking in nitrogen is that the organic component contained in the matrix component is carbonized. This was confirmed by the fact that when the black-fired product in nitrogen was further fired in air at 800 ° C. for 1 hour, it turned into the same white color as the air-fired product.

Further, the product fired in nitrogen had lower strength and higher elastic modulus than the product fired in air. This means that firing in air has a higher elongation than firing in nitrogen, thus indicating that the former is more tenacious than the latter.

(Example 17, Comparative Examples 1 to 3--Influence of Matrix Component I) The matrix composition was prepared by the method described in Example 1 using the matrix components and mixing ratios shown in Table 10. . The prepreg and the cured laminate (prepreg cured product) were manufactured by the methods described in Examples 4 and 8, respectively. For Example 17 and Comparative Example 1 shown in Table 10, each cured laminate was heated in air to 800 ° C. at a temperature increase rate of 1.5 ° C./min, held at that temperature for 1 hour, and fired and laminated. I made a board. The densification treatment was carried out by the method of Example 13.

[0223]

[Table 10]

In the comparison under the same method and under the same conditions, the following results were obtained.

Comparative Example 3: The prepreg impregnated with only the component (B) had almost no tackiness, and the fibers were twisted, and cutting was difficult as compared with the other examples. Also, when laminating the prepregs and curing using a hot press,
When the temperature was increased, the flow of the matrix (and the fiber) was too large, and the flow out of the mold made it impossible to produce a good laminate. Therefore, the firing operation in the next step could not be carried out.

Comparative Example 2: The prepreg impregnated with the components (A) and (B) had poor tackiness, but could be easily cut. However, the cured product after lamination and hot pressing peeled off the layers, and an integrated laminate could not be obtained. Therefore,
The firing operation in the next step could not be carried out.

Comparative Example 1 and Example 17: In Comparative Example 1, the prepreg had poor tackiness and was difficult to handle, but it was easy to cut, and the curing operation was good, and the prepreg was integrated. A cured laminate could be obtained.
In addition, in Example 17, all of the tackiness, cuttability, and curing operation were excellent, and a favorable cured laminate could be obtained.

Example 1 for these two cured laminates
Firing and densification treatment were carried out by the method described in 1 and Example 13. The measurement was performed with respect to the shrinkage rate during firing and the flexural strength, flexural modulus and hardness of the cured product, the fired product and the densified product. Hardness is Vickers hardness meter AVK-CT
(Manufactured by Akashi Seisakusho Co., Ltd.). The results are shown in Table 11.

[0229]

[Table 11]

The shrinkage percentage during firing is slightly higher in Example 17 than in Comparative Example 1. It is considered that this is due to the effect that the organic component (E) contained in the former is released during firing. However, in both cases, the shrinkage rate is extremely small, so it can be concluded that there is almost no dimensional change due to firing.

The clear difference between the two examples is due to the mechanical properties of the laminate. The flexural strength, flexural modulus, and Vickers hardness of each laminate at each of the curing, firing, and densification stages were significantly higher in Example 17 than in Comparative Example 1. This means that the excellent mechanical properties of the cured product produced are maintained after firing and after densification. In particular, it was confirmed that the densification treatment of Example 17 had a higher strength increasing effect than that of Comparative Example 1. That is,
The bending strength is improved by about 50% in the former case, but is only about 20% in the latter case. The reason for this is not clear, but it is presumed that the fired product obtained in the former has a higher porosity than the porosity, whereas that in the latter is higher than the porosity. It

The above results show that, when a cured product having a complicated shape is produced by using the method of Example 17, the prepreg has good tackiness and is easy to handle, and it is strong and hard. Even if a firing operation is applied under restraint, the shape does not collapse, that is, the self-shape-retaining property is effectively retained, and there is almost no dimensional change, that is, there is no collapse of the shape. It shows that the generation of cracks caused by shrinkage can be suppressed to a minimum, and as a result, a long fiber reinforced ceramic product having good mechanical properties can be manufactured. That is, the addition of the component (E) not only imparts excellent mechanical properties to the laminate at each stage and facilitates strength improvement by the densification treatment, but also imparts good tackiness and drapeability to the prepreg. It also serves to impart good mechanical properties to the product, as a result of which it improves the shaping properties.

Comparative Example 4--Influence of Matrix Component I
I) The prepreg, the prepreg cured product and the prepreg fired product were produced by the method described in Example 17. However, Example 1
Among the 7 matrix components, mullite was used in place of the alumina and titanium oxide that were the (A) component. The mixing ratio of mullite (3Al ₂ O ₃ .2SiO ₂ ) was the same as the total amount of alumina and titanium oxide. As the mullite, a powder having an average particle diameter of 1.2 μm (outside the range specified in the present invention) was used. The other components and the mixing ratio are the same as in Example 17.

When the matrix composition described in Example 17 was used, the laminated prepreg had a thickness of 1.8 mm when hot pressed, while the component (A) was changed to mullite powder, and the same conditions were obtained. The flow of the matrix was not recognized even by hot pressing, and the thickness stopped at 3.1 mm. Also. When the test piece was cut out from the fired laminated plate, it was almost broken, and even the test piece that was successfully cut out had a bending strength of 1.1 kg / mm ² and a bending elastic modulus of 1370 k.
The value was as low as g / mm ² . The reason for this is attributed to the large particle size rather than the oxide composition. This result is
It indicates that metal oxide fine particles having a particle size of 1 μm or less, preferably 0.5 μm or less should be used.

Example 18--Influence of Matrix Components III
) A prepreg, a prepreg cured product, a prepreg fired product, and a densified product were produced by the method described in Example 17. However, among the matrix components of Example 17,
The same amount of ethylene glycol dimethacrylate was used in place of trimethylolpropane trimethacrylate as the component (E). The bending strength of the laminate after densification is 2
0.2 kg / mm ² , flexural modulus 5980 kg / mm
^{Was 2} . These values are on the same level as the values obtained in Example 17, indicating that the latter compound is also sufficiently usable. However, compared to the former compound, the latter compound was not problematic in practical use, but it was confirmed that the tackiness was somewhat small.

(Comparative Examples 5 and 6--Comparison with Polymer Binder) In the conventional slurry method, polymer binders are often used. Therefore, polyurethane was used as the polymer, and this component was combined with the component (D) and the component (E) to examine this effect (Comparative Example 5). The component (C) was used instead of the polymer, and a system in which the component (D) and the component (E) were combined was also tested (Comparative Example 6).

The matrix composition was prepared by the method described in Example 1. Table 12 shows the mixing ratio of the matrix components.

[0238]

[Table 12]

A prepreg was produced according to the method described in Example 4 using the above matrix liquid and the alumina fiber woven fabric described in Example 4. The content rate of the matrix (solid content) was 60% by weight. This prepreg is 0 degrees,
Four pieces are laminated in the direction of 90 degrees and 1 by hot press
Molded and cured at 50 ° C. for 15 minutes under the condition of 3.5 kg / cm ² . After that, it was heated to 800 ° C. at a heating rate of 1.5 ° C./min in air under normal pressure and kept at that temperature for 1 hour.

When the matrix composition of Comparative Example 5 was used, there was no matrix flow,
It showed some tackiness and could be molded. However, when this was fired, the obtained fired product did not cause peeling of the layer, but only a soft product with no hardness and flexibility was obtained, and the matrix collapsed and fell off with a slight force. . If you use an organic binder,
It is considered that at normal pressure and low temperature firing, the force for binding the ceramic particles disappears after the thermal decomposition and release. When such an organic binder is used, it has been shown that the atmospheric pressure low temperature firing used in the present invention is unsuitable, and the high pressure high temperature sintering operation is required as used in the conventional slurry method. There is.

Also in Comparative Example 6, there was no matrix flow, but molding and curing were possible.
However, when this was fired, the four layers were peeled off. This indicates a lack of bonding force (binding force). Therefore, in order to achieve the objects and effects of the present invention, this result indicates that the components (A), (B), and (C) are required.
It shows that five components, the component (D) and the component (E), are essential components.

(Example 1) In the structure shown in FIG. 2, polyvinyl fluoride sheets were laminated on both sides of a sheet obtained by impregnating glass fiber with a phenol resin, and further, an epoxy adhesive was used to form the sheet of Example 12 above. A laminated structure formed by laminating ceramic long fiber reinforced ceramic material layers made of a densified ceramic laminated body was adopted.

Regarding this laminated structure, FAA Regulation 1
4 CFR Ch.1 (1-1-93 version) Section 25.853, Part 1 combustion test was conducted. In all of the vertical test, the horizontal test, and the 45 ° test, no burning or smoke of the sample was observed.

Comparative Example 1 A laminated structure having the same structure as that of the laminated structure shown in FIG. 2 except that the ceramic long fiber reinforced ceramic material and the epoxy adhesive are not provided. A combustion test similar to that in 1 was performed.

As a result of the combustion test, the polyvinyl fluoride sheet burned and smoked, and the sheet formed by impregnating glass fiber with the phenol resin was carbonized to the back side thereof.

Example 2 In the structure shown in FIG. 3, a sheet made of glass fiber impregnated with a phenol resin is laminated on both sides of an aluminum honeycomb, and a polyvinyl fluoride sheet is laminated on both sides of the sheet. A laminated structure was used in which ceramic long fiber reinforced ceramic material layers made of the densified ceramic laminated body of Example 12 were laminated via an epoxy adhesive.

Regarding this laminated structure, FAA Regulation 1
4 CFR Ch.1 (1-1-93 version) Section 25.853, Part 1 combustion test was conducted. In all of the vertical test, the horizontal test, and the 45 ° test, no burning or smoke of the sample was observed.

(Comparative Example 2) A laminated structure having the same structure as the laminated structure shown in FIG. 3 except that the ceramic long fiber reinforced ceramic material and the epoxy adhesive were not provided. A combustion test similar to that in 1 was performed.

As a result of the combustion test, the polyvinyl fluoride sheet burned and smoked, and the sheet formed by impregnating glass fiber with the phenol resin was carbonized to the back side thereof.

(Analysis of smoke and gas) A prepreg (MXB6820 / 7781 of Mitsubishi Chemical Co., Ltd.) obtained by impregnating glass fiber (181 style) with phenol resin was used by JI.
When the smoke emitted according to SK7217 was analyzed, the smoke contained 1075 mg / g of carbon dioxide, 25.5 mg / g of carbon monoxide, 41.4 mg / g of ethylene, and 3.4 mg / g of others. Was there. The smoke density of this prepreg was 124.00 when measured according to ASTM F814-846.

The above-mentioned Example 2 was added to the glass fiber (181 style).
Prepreg cured product obtained by curing a prepreg impregnated with the ceramic matrix of (Curing conditions: 150 ° C., 3
kg / cm ² , curing time of 15 minutes) according to JIS K721
When the smoke emitted according to No. 7 was analyzed, carbon dioxide in the smoke was 251.5 mg / g and carbon monoxide was 4.8 m.
g / g, ethylene 4.3 mg / g, others 1.7 m
g / g was included. In addition, this prepreg cured product is
The smoke density, measured according to STM F814-846, was 17.3.

The above-mentioned example 2 was added to the glass fiber (181 style).
Prepreg cured product obtained by curing a prepreg impregnated with the ceramic matrix of (Curing conditions: 150 ° C., 3
(kg / cm ² , curing time of 15 minutes) is further 60 in air.
When smoke produced by burning a product obtained by firing at 0 ° C. for 2 hours according to JIS K7217 is analyzed, carbon dioxide in the smoke is 0.1 mg / g or less, carbon monoxide is 1 mg / g or less, and ethylene is 1 mg / g. Below is 0.7mg / others
g or less was included. The smoke density of the fired product of this prepreg cured product was measured according to ASTM F814-846, and it was 0.17.

[0253]

According to the present invention, since the inner wall material and floor material using the ceramic long fiber reinforced ceramic material are used, it is possible to provide a vehicle and a building for protecting an occupant from a fire accident.

According to the present invention, by using a ceramic long fiber reinforced ceramic material, there is provided a honeycomb laminated structure suitable for use as a vehicle or a building capable of protecting personnel from a fire accident, or an interior article. can do.

[Brief description of drawings]

FIG. 1 is an explanatory longitudinal sectional view showing the inside of an aircraft.

FIG. 2 is a cross-sectional view showing a laminated structure which is an embodiment of the present invention.

FIG. 3 is a cross-sectional view showing a honeycomb laminated structure which is an embodiment of the present invention.

FIG. 4 is a sectional view showing a honeycomb laminated structure which is another embodiment of the present invention.

FIG. 5 is a cross-sectional view showing a honeycomb laminated structure which is still another embodiment of the present invention.

FIG. 6 is a partial cross-sectional perspective explanatory view showing a luggage storage shelf formed by using the honeycomb laminated structure according to the embodiment of the present invention.

FIG. 7 is an explanatory diagram showing an outline of a building which is an embodiment of the present invention.

FIG. 8 is a schematic perspective explanatory view showing interior parts of a building which is an embodiment of the present invention.

[Explanation of symbols]

1 ... passenger plane, 2 ... guest room 2, 3 ... inner wall, 4 ...
..Cargo compartments, 5 ... Floor materials, 6 ... Ceiling materials, 7 ...
Laminated structure, 8 ... Sheet made of heat resistant resin composition 8, 9 ... Flame retardant resin sheet, 10 ... Adhesive agent, 11 ... Ceramic long fiber reinforced ceramic material layer, 12 ... Honeycomb laminated structure, 13 ... Honeycomb, 14 ... Sheet formed of flame-retardant resin composition,
15 ... Flame-retardant resin sheet, 16 ... Adhesive, 17
... Ceramic long fiber reinforced ceramic materials, 18 ...
.Honeycomb laminated structure, 19 ... Honeycomb, 20 ...
-Sheet, 21 ... Ceramic long fiber reinforced ceramic material, 22 ... Decorative sheet, 23 ... Transparent protective sheet, 24 ... Aircraft, 25 ... Baggage storage rack, 26
... Shelves main body, 27 ... Opening / closing lid, 28 ... Buildings,
29 ... Wall body, 30 ... Floor material, 31 ... Beam material, 3
2 ... Ceiling material, 33 ... Oblique material, 34 ... Roofing material, 35 ... Ceiling panel, 36 ... Wall panel, 3
7 ... Floor panel, 38 ... Foundation floor panel, 39
... Door panel.

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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B32B 5/02 B 9349-4F B60R 13/02 Z B64C 1/00 B B64D 11/02 8816-3D C7 C08J 5/06 CFH E04C 2/36 G E04F 13/08 A 9127-2E // B29K 83:00 105: 08 505: 00 505: 02 B29L 31:30 C08L 83:00

Claims (27)

[Claims] 1. A vehicle having an inner wall material, wherein at least one of the inner wall material and the floor material is made of an inorganic long fiber reinforced ceramic material. 2. The inorganic long fiber reinforced ceramic material comprises:
2. The vehicle according to claim 1, wherein a prepreg comprising ceramic long fibers, a metal oxide, an organic polymer and / or a monomer that becomes the organic polymer, and a curing agent thereof is molded and cured. 3. The inorganic long fiber reinforced ceramic material comprises:
An inorganic fiber tow or an inorganic fiber product is impregnated with a liquid or sheet material of a matrix composition containing the following components (A), (B), (C), (D) and (E). Alternatively, the vehicle according to claim 1 or 2, wherein a prepreg formed by heating and permeating is molded and cured. (A) component; fine powder of metal oxide having an average particle size of 1 μm or less; (B) component; soluble siloxane polymer having a double chain structure; (C) component; at least 1 ethylenically unsaturated double bond.
Trifunctional silane compound in individual molecule, (D) component; organic peroxide, (E) component; at least 2 ethylenically unsaturated double bonds
Radical-polymerizable monomer in individual molecule 4. The matrix composition contains the component (A) in an amount of 350 to 750 parts by weight, the component (B) in an amount of 80 to 170 parts by weight, and the component (C) in an amount of 25 to 1 parts by weight.
The vehicle according to claim 3, wherein the amount of the component (D) is 25 parts by weight, the amount of the component (D) is 1 to 4 parts by weight, and the amount of the component (E) is 25 to 125 parts by weight. 5. The component (A) is an oxide or a complex oxide containing at least one selected from silica, alumina, and titanium oxide, and the component (B) is a polysilsesquioxane. The component (C) is γ-
(Meth) acryloxyalkyltrialkoxysilane, the component (D) is a peroxide having a temperature of 110 ° C. or higher for obtaining a half-life of 10 hours, and the component (E) is a polyhydric alcohol. Di (meth) acrylate and / or tri (meth) acrylate of a polyhydric alcohol, wherein the inorganic fibers are glass fibers, alumina fibers, silica fibers, tyranno fibers, and various types containing alumina and / or silica as a main component. The vehicle according to claim 3 or 4, wherein the vehicle is at least one selected from the group consisting of oxide-based inorganic fibers made of fibers. 6. The inorganic long fiber reinforced ceramic material comprises:
The surface of which is coated with a glaze burned product.
The vehicle according to any one of 5 above. 7. The method of claim 1, wherein the vehicle is an aircraft.
7. The vehicle according to any one of 6 to 6. 8. A honeycomb laminated structure in which an inorganic long fiber reinforced ceramic material is laminated on both sides or one side of a honeycomb. 9. The inorganic long fiber reinforced ceramic material comprises:
The honeycomb laminated structure according to claim 7, wherein the prepreg according to claim 2 or 3 is formed, cured, and then fired. 10. The inorganic long fiber reinforced ceramic material comprises the component (A) and the component (B) according to claim 3.
A liquid or sheet material of a matrix composition containing the component (C), the component (D) and the component (E) in the content ratios according to claim 4 is used as a tow of inorganic fibers or a product of inorganic fibers. The honeycomb laminated structure according to claim 9, wherein a prepreg formed by impregnation or heat infiltration is molded and cured. 11. The component (A) is silica, alumina,
Or an oxide or a composite oxide containing at least one selected from titanium oxide, wherein the component (B) is a polysilsesquioxane, and the component (C) is γ-
(Meth) acryloxyalkyltrialkoxysilane, the component (D) is a peroxide having a temperature of 110 ° C. or higher for obtaining a half-life of 10 hours, and the component (E) is a polyhydric alcohol. Di (meth) acrylate and / or tri (meth) acrylate of a polyhydric alcohol, wherein the inorganic fibers are glass fibers, alumina fibers, silica fibers, tyranno fibers, and various types containing alumina and / or silica as a main component. The honeycomb laminated structure according to claim 9 or 10, wherein the honeycomb laminated structure is at least one selected from the group consisting of oxide-based inorganic fibers made of fibers. 12. The honeycomb laminated structure according to any one of claims 9 to 11, wherein the surface of the inorganic long fiber reinforced ceramic material is coated with a glaze burned material. 13. An interior article comprising an inorganic long fiber reinforced ceramic material. 14. The interior article according to claim 13, wherein the inorganic long fiber reinforced ceramic material is obtained by molding and curing the prepreg according to claim 2 or 3. 15. The component (A), the component (B) according to claim 3, wherein the inorganic long fiber reinforced ceramic material is
A liquid or sheet material of a matrix composition containing the component (C), the component (D) and the component (E) in the content ratios according to claim 4 is used as a tow of inorganic fibers or a product of inorganic fibers. The interior article according to claim 14, wherein a prepreg formed by impregnation or heat infiltration is molded and cured. 16. The component (A) is silica, alumina,
Or an oxide or a composite oxide containing at least one selected from titanium oxide, wherein the component (B) is a polysilsesquioxane, and the component (C) is γ-
(Meth) acryloxyalkyltrialkoxysilane, the component (D) is a peroxide having a temperature of 110 ° C. or higher for obtaining a half-life of 10 hours, and the component (E) is a polyhydric alcohol. Di (meth) acrylate and / or tri (meth) acrylate of a polyhydric alcohol, wherein the inorganic fibers are glass fibers, alumina fibers, silica fibers, tyranno fibers, and various types containing alumina and / or silica as a main component. The interior article according to claim 14 or 15, which is at least one selected from the group consisting of oxide-based inorganic fibers made of fibers. 17. The interior component according to any one of claims 13 to 16, wherein the surface of the inorganic long fiber reinforced ceramic material is coated with a baked product of glaze. 18. A panel comprising an inorganic long fiber reinforced ceramic material. 19. The panel according to claim 18, wherein the inorganic long fiber reinforced ceramic material is obtained by molding and curing the prepreg according to claim 2 or 3. 20. The inorganic long fiber reinforced ceramic material comprises the component (A) and the component (B) according to claim 3.
A liquid or sheet material of a matrix composition containing the component (C), the component (D) and the component (E) in the content ratios according to claim 4 is used as a tow of inorganic fibers or a product of inorganic fibers. 20. The panel according to claim 19, which is obtained by molding a prepreg formed by impregnation or heat infiltration and curing the prepreg. 21. The component (A) is silica, alumina,
Or an oxide or a composite oxide containing at least one selected from titanium oxide, wherein the component (B) is a polysilsesquioxane, and the component (C) is γ-
(Meth) acryloxyalkyltrialkoxysilane, the component (D) is a peroxide having a temperature of 110 ° C. or higher for obtaining a half-life of 10 hours, and the component (E) is a polyhydric alcohol. Di (meth) acrylate and / or tri (meth) acrylate of a polyhydric alcohol, wherein the inorganic fiber is glass fiber, alumina fiber, silica fiber, tyranno fiber, and various types containing alumina and / or silica as a main component. The panel according to claim 19 or 20, wherein the panel is at least one selected from the group consisting of oxide-based inorganic fibers made of fibers. 22. The panel according to any one of claims 18 to 21, wherein the surface of the inorganic long fiber reinforced ceramic material is coated with a baked product of glaze. 23. A building provided with an inner wall material, wherein the inner wall material uses an inorganic long fiber reinforced ceramic material. 24. The building according to claim 24, wherein the inorganic long fiber reinforced ceramic material is obtained by molding and curing the prepreg according to claim 2 or 3. 25. The inorganic long fiber reinforced ceramic material comprises the component (A) and the component (B) according to claim 3.
A liquid or sheet material of a matrix composition containing the component (C), the component (D) and the component (E) in the content ratios according to claim 4 is used as a tow of inorganic fibers or a product of inorganic fibers. The building according to claim 24, wherein the prepreg formed by impregnation or heat infiltration is formed, cured, and then fired. 26. The component (A) is silica, alumina,
Or an oxide or a composite oxide containing at least one selected from titanium oxide, wherein the component (B) is a polysilsesquioxane, and the component (C) is γ-
(Meth) acryloxyalkyltrialkoxysilane, the component (D) is a peroxide having a temperature of 110 ° C. or higher for obtaining a half-life of 10 hours, and the component (E) is a polyhydric alcohol. Di (meth) acrylate and / or tri (meth) acrylate of a polyhydric alcohol, wherein the inorganic fibers are glass fibers, alumina fibers, silica fibers, tyranno fibers, and various types containing alumina and / or silica as a main component. The interior article according to claim 24 or 25, which is at least one selected from the group consisting of oxide-based inorganic fibers made of fibers. 27. The building according to any one of claims 22 to 26, wherein the surface of the inorganic long fiber reinforced ceramic material is coated with a glaze burned material.